Second-order nonlinear optical compound and nonlinear optical element comprising the same

ABSTRACT

Problem to Be Solved: to provide a chromophore having a far superior nonlinear optical activity to conventional chromophores and to provide a nonlinear optical element comprising said chromophore. 
     Solution: a chromophore comprising a donor structure D, a π-conjugated bridge structure B, and an acceptor structure A, the donor structure D comprising an aryl group substituted with a substituted oxy group; and a nonlinear optical element comprising said chromophore.

TECHNICAL FIELD

The present invention relates to a nonlinear optical compound, anonlinear optical material comprising the nonlinear optical compound,and a nonlinear optical element comprising the nonlinear opticalcompound.

BACKGROUND ART

Nonlinear optical materials can change the intensity and phase of lightin response to an external field such as an electric field and amagnetic field and are therefore practically used as optical controlelements in optical communication equipment, laser apparatus, and thelike. Inter alia, devices such as optical modulators, optical switches,and optical memories utilize the electrooptic effect of non-linearoptical materials.

Conventionally, as nonlinear optical materials, inorganic materials suchas lithium niobate and potassium dihydrogen phosphate have been widelyused. However, the demands for higher nonlinear optical performance,manufacturing cost reduction, composites with an electronic integratedcircuit, and the like have led to increased attention on organicnonlinear optical materials and various investigations into theirpractical use have been conducted, as described in “Hisenkei Kougaku NoTamen° Yuuki Zairyo (Organic Materials for Nonlinear Optics)”, edited bythe Chemical Society of Japan, KIKAN KAGAKU SOSETSU No. 15 (1992);“Organic Nonlinear Optical Materials”, Ch. Bosshard, et al., Gordon andBreach Publishers (1995); and “Joho, Tsushin Yo Hikari Yuuki Zairyo NoSaishin Gijutsu (The Newest Technology of Optical Organic Materials forInformation and Telecommunication)”, supervised by Toshikuni Kaino, CMCPublishing CO., LTD., 2007.

Organic nonlinear optical materials are obtainable by dispersing in orbinding to a host material (e.g., a polymeric material) a compoundhaving nonlinear optical activity (hereinafter simply referred to as a“nonlinear optical compound”). A known nonlinear optical compound thatexhibits the electrooptic effect is a push-pull π-conjugated compoundhaving an electron donor group (donor structure D) and an electronacceptor group (acceptor structure A), which are present at either endof the molecular structure, as well as a π-conjugated chain(π-conjugated bridge structure B) that connects said groups. Forexample, U.S. Pat. No. 6,067,186 describes a nonlinear optical compoundhaving a thiophene ring in a π-conjugated bridge structure B, asrepresented by the following formula:

JP 2004-501159 T describes an attempt to improve the performance of anonlinear optical compound by employing a predetermined group as anacceptor structure A. “Large Electro-optic Activity and Enhanced ThermalStability from Diarylaminophenyl-Containing High-β Nonlinear OpticalChromophores.” Y. J. Cheng, et al., Chem. Mater. Vol. 19, 1154 (2009)also describes an attempt to improve the performance of a nonlinearoptical compound by employing a predetermined group as a donor structureD.

SUMMARY OF INVENTION Technical Problem

In production of an optical element having an optical waveguide made ofa nonlinear optical material, orientation processing is sometimesperformed on the nonlinear optical compound to produce the second-ordernonlinear optical activity of the nonlinear optical material. Generallythe method used for orienting a nonlinear optical compound is electricfield poling. In electric field poling, an electric field is applied toa nonlinear optical material and, by the Coulomb force between thedipole moment of the nonlinear optical compound and the applied electricfield, the nonlinear optical compound is oriented toward the appliedelectric field direction.

In electric field poling, usually a nonlinear optical material is heatedto near the glass transition temperature of its host material so thatthe molecular motion in the nonlinear optical compound is accelerated,and an electric field is then applied to the material. Therefore, inorder to obtain a nonlinear optical element that achieves an excellentnonlinear optical performance, it is necessary to use a nonlinearoptical compound that has, besides an excellent nonlinear opticalproperty, heat resistance sufficient to prevent the compound fromdeteriorating when heated in orientation processing.

Further, because of demands for the high-speed performance of electroniccircuits, attempts have been made to increase the rate of signaltransmission by connecting electronic circuits with an optical circuitand investigations have been conducted into the use of an electroopticelement made of a nonlinear optical material in electric-optical signalconversion. In this conversion, the temperature of the electroniccircuit that operates at a high rate becomes high, and the molecularmotion in the nonlinear optical compound thus increases, which mightrelax the orientation. Therefore the host material is required to havehigher glass transition temperature and accordingly the nonlinearoptical compound is required to have higher heat resistance.

The present invention has been made in light of the above circumstances,and an object of the present invention is to provide a nonlinear opticalcompound that can achieve a sufficiently high level of both a nonlinearoptical property and heat resistance by utilizing a donor structure Dthat can improve the nonlinear optical property without significantlydeteriorating the heat resistance.

Another object of the present invention is to provide a nonlinearoptical material utilizing the nonlinear optical compound and to providea nonlinear optical element utilizing the nonlinear optical compound.

Another object of the present invention is to provide a chromophorehaving a far superior nonlinear optical activity to conventionalchromophores and to provide a nonlinear optical element comprising saidchromophore.

Solution to Problem

The inventors have conducted extensive research to solve the aboveproblems and, as a result, found out that a chromophore comprising adonor structure D, π-conjugated bridge structure B, and an acceptorstructure A has a far superior nonlinear optical activity toconventional chromophores when the donor structure D contains asubstituted oxyaryl, and thus the present invention has been completed.

That is, the present invention relates to:

<1> a chromophore comprising a donor structure D, a π-conjugated bridgestructure B, and an acceptor structure A, the donor structure Dcomprising an aryl group substituted with a substituted oxy group andthe acceptor structure A being free of —SO₂—;<2> the chromophore according to the above <1>, wherein the substitutedoxy group is attached to an ortho-carbon atom of the aryl group or to anortho-carbon atom and the para-carbon atom of the aryl group;<3> the chromophore according to the above <1> or <2>, wherein the arylgroup may be further substituted with an optionally substituted aminogroup;<4> the chromophore according to any of the above <1> to <3>, whereinthe π-conjugation of the π-conjugated bridge structure B is acarbon-carbon conjugation;<5> the chromophore according to any of the above <1> to <4>, whereinthe chromophore is represented by the formula D-B-A, wherein Drepresents the donor structure D, B represents the π-conjugated bridgestructure B, and A represents the acceptor structure A;<6> the chromophore according to any of the above <1> to <5>, whereinthe donor structure D is represented by the formula D-1:

wherein

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and R_(D) ¹ represents analkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group,an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group,or a hydroxy group, and R_(D) ¹ may have a substituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent); and

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

<7> the chromophore according to any of the above <1> to <6>, whereinthe donor structure D is represented by the formula D-1-1:

wherein

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent;

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ² and R_(D) ³ each mayhave the same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent); and

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

<8> the chromophore according to any of the above <1> to <6>, whereinthe donor structure D is represented by the formula D-1-2:

wherein

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and R_(D) ¹ represents analkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group,an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group,or a hydroxy group, and R_(D) ¹ may have a substituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent); and

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a saturated heterocyclic ring optionally having asubstituent, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, with the aryl carbon atom to which said nitrogen atom isattached, and with the aryl carbon atom which is adjacent to said carbonatom, a heterocyclic ring containing the nitrogen atom as a hetero atomand optionally having a substituent;

<9> the chromophore according to any of the above <1>, <2>, <4> and <5>,wherein the donor structure D is represented by the formula D-2:

wherein

at least one of R_(D) ¹, R_(D) ² and R_(D) ³ independently represents analkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group,an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group,or a hydroxy group; the rest independently represent a hydrogen atom oran alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may have the sameor different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and R_(D) ¹ represents analkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group,an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group,or a hydroxy group, and R_(D) ¹ may have a substituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent);

<10> the chromophore according to any of the above <1>, <2>, <4>, <5>and <9>, wherein the donor structure D is represented by the formulaD-2-1:

wherein

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent; and

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ² and R_(D) ³ each mayhave the same or different substituents (when R_(D) ² and R_(D) ³ areeach attached to adjacent carbon atoms of the aryl of the donorstructure D,

R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent);

<11> the chromophore according to any of the above <1> to <10>, whereinthe acceptor structure A is represented by the formula selected from thegroup consisting of:

wherein

Y represents —CR_(A) ¹R_(A) ²—, —O—, —S—, —SO—, —SiR_(A) ¹R_(A) ²—, —NR—(wherein R represents a hydrogen atom or an alkyl group), or —C(═CH₂)—;and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, analkoxy group, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A)² each may have the same or different substituents, or

R_(A) ¹ and R_(A) ² form, together with the carbon atom to which theyare attached, a structure that may have a substituent and is representedby the following formula:

<12> the chromophore according to any of the above <1> to <11>, whereinthe carbon-carbon conjugated bridge structure B may have a substituentand is represented by the formula selected from the group consisting of:

wherein

R_(B) ¹ to R_(B) ⁸ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryl group, an alkenyl group, a cycloalkylgroup, a cycloalkenyl group, a haloalkyl group, an aralkyl group, anaryloxy group, or an aralkyloxy group, and R_(B) ¹ to R_(B) ⁸ each mayhave the same or different substituents;

n represents an integer of 1 to 5; and

m and m′ independently represent an integer of 0 to 3;

<13> the chromophore according to any of the above <1> to <12>, whereinthe carbon-carbon conjugated bridge structure B is represented by theformula B-I:

wherein

π¹ and π² independently represent the same or different carbon-carbonconjugated π-bonds, and π¹ and π² each may have the same or differentsubstituents; and

R_(B) ¹ and R_(B) ² independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryl group, an alkenyl group, a cycloalkylgroup, a cycloalkenyl group, a haloalkyl group, an aralkyl group, anaryloxy group, or an aralkyloxy group, and R_(B) ¹ and R_(B) ² each mayhave the same or different substituents;

<14> the chromophore according to any of the above <1> to <6> and <11>to <13>, wherein the chromophore is represented by the formula I-1:

wherein

π¹ and π² independently represent the same or different carbon-carbonconjugated π-bonds, and π¹ and π² each may have the same or differentsubstituents;

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

R_(B) ¹ and R_(B) ² independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryl group, an aralkyl group, an aryloxygroup, or an aralkyloxy group, and R_(B) ¹ and R_(B) ² each may have thesame or different substituents; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents;

<15> the chromophore according to any of the above <1> to <7> and <11>to <14>, wherein the chromophore is represented by the formula I-1-1:

wherein

π¹ and π² independently represent the same or different carbon-carbonconjugated π-bonds, and π¹ and π² each may have the same or differentsubstituents;

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent;

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ² and R_(D) ³ each mayhave the same or different substituents (when R_(D) ² and R_(D) ³ areeach attached to adjacent carbon atoms of the aryl of the donorstructure D,

R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

R_(B) ¹ and R_(B) ² independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryl group, an aralkyl group, an aryloxygroup, or an aralkyloxy group, and R_(B) ¹ and R_(B) ² each may have thesame or different substituents; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents;

<16> the chromophore according to any of the above <1>, <2>, <4>, <5>,<9> and <11> to <13>, wherein the chromophore is represented by theformula I-2:

wherein

π¹ and π² independently represent the same or different carbon-carbonconjugated π-bonds, and π¹ and π² each may have the same or differentsubstituents;

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and R_(D) ¹ represents analkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group,an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group,or a hydroxy group, and R_(D) ¹ may have a substituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent);

R_(B) ¹ and R_(B) ² independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryl group, an aralkyl group, an aryloxygroup, or an aralkyloxy group, and R_(B) ¹ and R_(B) ² each may have thesame or different substituents; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents;

<17> the chromophore according to any of the above <1> to <12>, whereinthe carbon-carbon conjugated bridge structure B is represented by theformula B-II:

wherein

π¹ and π² independently represent the same or different carbon-carbonconjugated π-bonds, and π¹ and π² each may have the same or differentsubstituents; and

R_(B) ¹, R_(B) ², R_(B) ³, and R_(B) ⁴ independently represent ahydrogen atom, an alkyl group, an alkoxy group, an aryl group, analkenyl group, a cycloalkyl group, a cycloalkenyl group, a haloalkylgroup, an aralkyl group, an aryloxy group, or an aralkyloxy group, andR_(B) ¹, R_(B) ², R_(B) ³ and R_(B) ⁴ each may have the same ordifferent substituents;

<18> the chromophore according to any of the above <1> to <6>, <11>,<12>, and <17>, wherein the chromophore is represented by the formulaII-1:

wherein

π¹ and π² independently represent the same or different carbon-carbonconjugated π-bonds, and π¹ and π² each may have the same or differentsubstituents;

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and R_(D) ¹ represents analkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group,an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group,or a hydroxy group, and R_(D) ¹ may have a substituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

R_(B) ¹, R_(B) ², R_(B) ³, and R_(B) ⁴ independently represent ahydrogen atom, an alkyl group, an alkoxy group, an aryl group, anaralkyl group, an aryloxy group, or an aralkyloxy group, and R_(B) ¹,R_(B) ², R_(B) ³, and R_(B) ⁴ each may have the same or differentsubstituents; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents;

<19> the chromophore according to any of the above <1> to <7>, <11>,<12>, <17>, and <18>, wherein the chromophore is represented by theformula II-1-1:

wherein

π¹ and π² independently represent the same or different carbon-carbonconjugated n-bonds, and π¹ and π² each may have the same or differentsubstituents;

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent;

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ² and R_(D) ³ each mayhave the same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

R_(B) ¹, R_(B) ², R_(B) ³, and R_(B) ⁴ independently represent ahydrogen atom, an alkyl group, an alkoxy group, an aryl group, anaralkyl group, an aryloxy group, or an aralkyloxy group, and R_(B) ¹,R_(B) ², R₃ ³, and R_(B) ⁴ each may have the same or differentsubstituents; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents;

<20> the chromophore according to any of the above <1> to <12>, whereinthe carbon-carbon conjugated bridge structure B is represented by theformula B-III:

wherein

m and m′ independently represent an integer of 0 to 3; and

R_(B) ¹, R_(B) ² and R_(B) ³ independently represent a hydrogen atom, analkyl group, an alkoxy group, an aryl group, an alkenyl group, acycloalkyl group, a cycloalkenyl group, a haloalkyl group, an aralkylgroup, an aryloxy group, or an aralkyloxy group, and R_(B) ¹, R_(B) ²and R_(B) ³ each may have the same or different substituents;

<21> the chromophore according to any of the above <1> to <6>, <11>,<12>, and <20>, wherein the chromophore is represented by the formulaIII-1:

wherein

m and m′ independently represent an integer of 0 to 3;

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

R_(B) ¹, R_(B) ², and R_(B) ³ independently represent a hydrogen atom,an alkyl group, an alkoxy group, an aryl group, an aralkyl group, anaryloxy group, or an aralkyloxy group, and R_(B) ¹, R_(B) ², and R_(B) ³each may have the same or different substituents; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents;

<22> the chromophore according to any of the above <1> to <7>, <11>,<12>, <20>, and <21>, wherein the chromophore is represented by theformula III-1-1:

wherein

m and m′ independently represent an integer of 0 to 3;

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent;

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ² and R_(D) ³ each mayhave the same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

R_(B) ¹, R_(B) ², and R_(B) ³ independently represent a hydrogen atom,an alkyl group, an alkoxy group, an aryl group, an aralkyl group, anaryloxy group, or an aralkyloxy group, and R_(B) ¹, R_(B) ², and R_(B) ³each may have the same or different substituents; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents;

<23> the chromophore according to any of the above <1> to <12>,wherein the carbon-carbon conjugated bridge structure B is representedby the formula B-IV:

wherein n represents an integer of 1 to 5;<24> the chromophore according to any of the above <1> to <6>, <11>,<12>, and <23>, wherein the chromophore is represented by the formulaIV-1-a:

wherein

n represents an integer of 1 to 5;

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent;

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ² and R_(D) ³ each mayhave the same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents;

<25> the chromophore according to any of the above <1> to <6>, <11>,<12>, and <23>, wherein the chromophore is represented by the formulaIV-1-b:

wherein

n represents an integer of 1 to 5;

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent;

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ² and R_(D) ³ each mayhave the same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents;

<26> the chromophore according to any of the above <1>, <2>, <4>, <5>,<9>, <11>, <12> and <23>, wherein the chromophore is represented by theformula IV-2-a:

wherein

n represents an integer of 1 to 5;

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ² and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent); and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents;

<27> the chromophore according to any of the above <1>, <2>, <4>, <5>,<9>, <11>, <12> and <23>, wherein the chromophore is represented by theformula IV-2-b:

wherein

n represents an integer of 1 to 5;

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent); and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents;

<28> the chromophore according to any of the above <6> to <10>, <14> to<16>, <18>, <19>, <21>, <22> and <24> to <27>,wherein

R_(D) ¹ represents a C₁₋₆ alkoxy group, a benzyloxy group, a silyloxygroup, a C₂-C₆ alkenyloxy group, a C₂₋₆ alkenylcarbonyloxy group, a C₃₋₆alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent; and

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, a C₁₋₆alkoxy group, a benzyloxy group, a silyloxy group, a C₂₋₆ alkenyloxygroup, a C₂₋₆ alkenylcarbonyloxy group, a C₃₋₆ alkynyloxy group, or ahydroxy group, and R_(D) ² and R_(D) ³ each may have the same ordifferent substituents;

<29> the chromophore according to any of the above <6> to <8>, <14>,<15>, <18>, <19>, <21>, <22>, <24>, and <25>,wherein

R_(D) ⁴ and R_(D) ⁵ independently represent an alkyl group, ahydroxyalkyl group, or a silyloxyalkyl group, and R_(D) ⁴ and R_(D) ⁵each may have the same or different substituents;

<30> the chromophore according to any of the above <11>, <14> to <16>,<18>, <19>, <21>, <22>, <24>, <25>, <26>, and <27>, wherein

R_(A) ¹ and R_(A) ² independently represent a methyl group, atrifluoromethyl group, or a phenyl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents;

<31> the chromophore according to any of the above <13> to <19>, wherein

π¹ and π² are each represented by the following formula:

and π¹ and π² each may have the same or different substituents;<32> the chromophore according to any of the above <13> to <19>, wherein

π¹ and π² are represented by the following formula:

andπ¹ and π² each may have the same or different substituents;<33> the chromophore according to any of the above <1> to <7>, <11> to<15>, and <28> to <32>, wherein the chromophore is represented by theformula selected from the group consisting of:

<34> the chromophore according to any of the above <1>, <2>, <4>, <5>,<9> to <13>, <16>, and <28> to <32>, wherein the chromophore isrepresented by the following formula:

<35> the chromophore according to any of the above <1> to <7>, <11>,<12>, <17> to <19>, and <28> to <32>, wherein the chromophore isrepresented by the formula selected from the group consisting of:

<36> the chromophore according to any of the above <1> to <7>, <11>,<12>, <20> to <22>, and <28> to <30>, wherein the chromophore isrepresented by the formula selected from the group consisting of:

<37> the chromophore according to any of the above <1> to <7>, <11>,<12>, <23>, <24>, <28> to <30>, wherein the chromophore is representedby the formula selected from the group consisting of:

<38> the chromophore according to any of the above <1> to <7>, <11> to<15>, and <28> to <31>, wherein the chromophore is represented by theformula selected from the group consisting of:

<39> the chromophore according to any of the above <1> to <7>, <11>,<12>, <25>, and <28> to <30>, wherein the chromophore is represented bythe following formula:

<40> the chromophore according to any of the above <1>, <2>, <4>, <5>,<9> to <12>, <26>, <28>, and <30>, wherein the chromophore isrepresented by the following formula:

and<41> the chromophore according to any of the above <1>, <2>, <4>, <5>,<9> to <12>, <27>, <28>, and <30>, wherein the chromophore isrepresented by the following formula:

The present invention also relates to:

<42> a nonlinear optical material comprising the chromophore accordingto any of the above <1> to <41> and a host material in which thechromophore is dispersed; and<43> the nonlinear optical material according to the above <42>, whereinthe host material comprises a resin having a reactive functional groupcapable of forming a covalent bond with the chromophore, and at leastpart of the chromophore is attached to the resin.

The present invention further relates to:

<44> a nonlinear optical element having a film formed from thechromophore according to any of the above <1> to <41> or the nonlinearoptical material according to the above <42> or <43>;<45> a nonlinear optical element having an optical waveguide formed fromthe chromophore according to any of the above <1> to <41> or thenonlinear optical material according to the above <42> or <43>; and<46> a nonlinear optical element comprising the chromophore according toany of the above <1> to <41>.

Advantageous Effects of Invention

By employing an aryl group substituted with a substituted oxy group inthe donor structure D, the nonlinear optical property of the nonlinearoptical compound of the present invention is improved withoutsignificant deterioration of the heat resistance. A material containingsuch a nonlinear optical compound exhibiting a larger nonlinear opticaleffect can give a nonlinear optical element that can change theintensity and phase of light in response to even a weaker external fieldapplied thereto.

When such a nonlinear optical element is used in, for example, anoptical modulator utilizing the electrooptic effect, the opticalmodulator can be driven by lower electric power, which makes possibleenergy saving and miniaturization. In addition, since the element has alarger nonlinear optical effect, which can change the intensity andphase of light in response to even a weaker electric field appliedthereto, the element can be used for an electric field sensor thatmeasures a leaked electric field of an electronic integrated circuit orfor a sensor for terahertz electromagnetic waves. Further, the elementin combination with an electronic circuit can be used for, for example,optical signal transmission between electronic circuits (See, forexample, “Low (Sub-1-Volt) Halfwave Voltage Polymeric Electro-opticModulators Achieved by Controlling Chromophore Shape.” Y. Shi, et al.,Science, vol. 288, 119 (2000)).

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic sectional view of an optical waveguide that is anembodiment of the nonlinear optical element of the present invention.

DESCRIPTION OF EMBODIMENTS

The definition of the terms used herein will be given below and thepresent invention will be explained in more detail.

Donor Structure D

The “donor structure D” of the present invention is not particularlylimited as long as it contains an aryl group substituted with asubstituted oxy group.

The term “substituted oxy group” as used herein refers to a structure inwhich a hydroxy group (—OH) is substituted with a substituent or thehydrogen atom of a hydroxy group is replaced with a substituent.

The “aryl group” in the above “aryl group substituted with a substitutedoxy group” includes a monocyclic aromatic hydrocarbon group (hereinafterreferred to as a monocyclic aryl group) and a polycyclic aromatichydrocarbon group (hereinafter referred to as a polycyclic aryl group).

The “monocyclic aryl group” is, for example, preferably a C₅₋₁₀ ringgroup, more preferably a C₅₋₇ ring group, further preferably a C₅₋₆ ringgroup, most preferably a C₆ ring group (namely, a phenyl group). Forexample, a C₅₋₁₀ ring means that the number of carbon atoms forming thering is 5 to 10, and the same applies to the other ring groups mentionedabove.

The “polycyclic aryl group” includes, for example, a two-ring fused arylgroup and a three-ring fused aryl group. The two-ring fused aryl groupis, for example, preferably a C₈₋₁₂ ring group and the like, morepreferably a C₉₋₁₀ ring group and the like, most preferably a C₁₀ ringgroup (namely, a naphthyl group) and the like.

Examples of the “substituent” in the above “substituted oxy group”include (1) an alkyl group optionally having a substituent, (2) ahaloalkyl group optionally having a substituent, (3) an aryl groupoptionally having a substituent, (4) a heteroaryl group optionallyhaving a substituent, (5) an aralkyl group optionally having asubstituent, (6) a silyl group optionally having a substituent, (7) analkenyl group optionally having a substituent, (8) an alkynyl groupoptionally having a substituent, (9) an acyl group optionally having asubstituent, and (10) an alkenylcarbonyl group optionally having asubstituent.

The “alkyl group” in the above “(1) an alkyl group optionally having asubstituent” includes a linear or branched C₁₋₂₀ alkyl group. The term“C₁₋₂₀ alkyl group” refers to an alkyl group in which the number ofcarbon atoms forming the group is 1 to 20, and the same applies to theother groups. Examples of the alkyl group include a methyl group, anethyl group, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group,an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, an undecyl group, a dodecylgroup, a tridecyl group, a tetradecyl group, a pentadecyl group, ahexadecyl group, a heptadecyl group, an octadecyl group, a nonadecylgroup, and an icosyl group. Preferred examples of the alkyl groupinclude a C₁₋₆ alkyl group. More preferred examples of the alkyl groupinclude a methyl group, an ethyl group, an n-propyl group, an isopropylgroup, an n-butyl group, an isobutyl group, a sec-butyl group, atert-butyl group, a pentyl group, an isopentyl group, a hexyl group, andan isohexyl group.

The “haloalkyl group” in the above “(2) a haloalkyl group optionallyhaving a substituent” includes a linear or branched C₁₋₂₀ alkyl groupsubstituted with at least one halogen atom (for example, a fluorineatom, a chlorine atom, a bromine atom, an iodine atom, or the like)which may be the same as or different from each other. Preferredexamples of the haloalkyl group include a halo C₁₋₆ alkyl group. Morepreferred examples of the haloalkyl group include a fluoromethyl group,a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group,a 1,2-difluoroethyl group, a chloromethyl group, a 2-chloroethyl group,a 1,2-dichloroethyl group, a bromomethyl group, a 2-bromoethyl group, a1-bromopropyl group, a 2-bromopropyl group, a 3-bromopropyl group, andan iodomethyl group.

The “aryl group” in the above “(3) an aryl group optionally having asubstituent” includes the same aryl group as the “aryl group” in theabove substituted oxyaryl. Examples of the aryl group include a phenylgroup and a naphthyl group.

The “heteroaryl group” in the above “(4) an heteroaryl group optionallyhaving a substituent” includes (a) a 5- or 6-membered monocyclicaromatic heterocyclic group containing 1 or more, preferably 1 to 3, thesame or different hetero atoms selected from the group consisting of anoxygen atom, a nitrogen atom, and a sulfur atom; (b) a fused-ringaromatic heterocyclic group obtainable by condensation of saidmonocyclic aromatic heterocyclic group with an aryl group (for example,an aryl group the same as the “aryl group” in the above substitutedoxyaryl, or the like); and (c) a fused-ring aromatic heterocyclic groupobtainable by condensation of the same or different monocyclic aromaticheterocyclic groups. Examples of the heteroaryl group include a pyrrolylgroup, a furyl group, a thienyl group, an imidazolyl group, a pyrazolylgroup, a thiazolyl group, an isothiazole group, an oxazolyl group, atriazolyl group, a tetrazolyl group, an oxadiazolyl group, a thiadiazolegroup, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, apyridazinyl group, a triazinyl group, an indolyl group, a benzofuranylgroup, a benzothienyl group, a benzimidazolyl group, a benzoxazolylgroup, a benzisoxazolyl group, a benzothiadiazolyl group, abenzisothiadiazolyl group, an indazolyl group, a purinyl group, aquinolyl group, an isoquinolyl group, a phthalazinyl group, anaphthyridinyl group, a quinoxalinyl group, a quinazolyl group, acinnolinyl group, a pteridinyl group, and a pyrido[3,2-b]pyridyl group.

The “aralkyl group” in the above “(5) an aralkyl group optionally havinga substituent” includes an alkyl group substituted with at least onearyl group. Examples of the aryl group include the “aryl group” in theabove substituted oxyaryl. Examples of the “alkyl group” include the“alkyl group” in the above “(1) an alkyl group optionally having asubstituent”. Examples of the aralkyl group include a benzyl group, a1-phenylethyl group, a phenethyl group, a 1-naphthylmethyl group, a2-naphthylmethyl group, a 1-naphthylethyl group, and a 2-naphthylethylgroup.

The “alkenyl group” in the above “(7) an alkenyl group optionally havinga substituent” includes a linear or branched C₂₋₂₀ alkenyl group.Preferred examples of the “alkenyl group” include a C₂₋₆ alkenyl group.More preferred examples of the alkenyl group include an ethenyl group, a1-propenyl group, a 2-propenyl group, a 1-methylethenyl group, a1-butenyl group, a 2-butenyl group, a 3-butenyl group, a1-methyl-1-propenyl group, a 1-methyl-2-propenyl group, a2-methyl-1-propenyl group, and a 2-methyl-2-propenyl group.

The “alkynyl group” in the above “(8) an alkynyl group optionally havinga substituent” includes a linear or branched C₃₋₂₀ alkynyl group.Preferred examples of the alkynyl group include a C₃₋₆ alkynyl group.More preferred examples of the alkynyl group include a 2-propynyl group,a 1-methyl-2-propynyl group, a 1,1-dimethyl-2-propynyl group, a2-butynyl group, a 3-butynyl group, a 1-pentynyl group, a 2-pentynylgroup, a 3-pentynyl group, and a 4-pentynyl group.

The “acyl group” in the above “(9) an acyl group optionally having asubstituent” includes a linear or branched C₁₋₂₀ acyl group. Preferredexamples of the “acyl group” include a C₁₋₆ acyl group. More preferredexamples of the “acyl group” include a formyl group, an acetyl group, apropionyl group, a butyryl group, an isobutyryl group, a valeryl group,an isovaleryl group, and a pivaloyl group.

The “alkenyl” in the above “(10) an alkenylcarbonyl group optionallyhaving a substituent” include, for example, the “alkenyl group” in theabove “(7) an alkenyl group optionally having a substituent”.

The “substituent” in the above “(1) an alkyl group optionally having asubstituent”, “(2) a haloalkyl group optionally having a substituent”,“(3) an aryl group optionally having a substituent”, “(4) a heteroarylgroup optionally having a substituent”, “(5) an aralkyl group optionallyhaving a substituent”, “(6) a silyl group optionally having asubstituent”, “(7) an alkenyl group optionally having substituent”, “(8)an alkynyl group optionally having a substituent”, “(9) an acyl groupoptionally having a substituent”, and “(10) an alkenylcarbonyl groupoptionally having a substituent” is not particularly limited andexamples of the substituent include an alkyl group, a haloalkyl group,an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, ahydroxy group, an oxiranyl group, a mercapto group, an amino group, acarbamoyl group, a sulfamoyl group, a carboxy group, an alkoxycarbonylgroup, a sulfo group, a sulfide group, a phosphono group, a nitro group,a cyano group, an amidino group, an imino group, a dihydroborono group,a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, aniodine atom, or the like), a sulfinyl group, a sulfonyl group, an acylgroup, an oxo group, and a thioxo group. The “substituent” may be onesubstituent or two or more substituents which may be the same as ordifferent from each other.

The “alkyl group”, the “haloalkyl group”, the “aryl group”, the “alkenylgroup”, the “alkynyl group”, and the “acyl group” as the above“substituent” are, for example, the “alkyl group” in the above “(1) analkyl group optionally having a substituent”, the “haloalkyl group” inthe above “(2) a haloalkyl group optionally having a substituent”, the“aryl group” in the above “(3) an aryl group optionally having asubstituent”, the “alkenyl group” in the above “(7) an alkenyl groupoptionally having a substituent”, the “alkynyl group” in the above “(8)an alkynyl group optionally having a substituent”, and the “acyl group”in the above “(9) an acyl group optionally having a substituent”,respectively.

Preferred examples of the “substituted oxy group” in the presentinvention include (a) an alkoxy group optionally having a substituent,(b) an aryloxy group optionally having a substituent, (c) an aralkyloxygroup optionally having a substituent, (d) a silyloxy group optionallyhaving a substituent, (e) an alkenyloxy group optionally having asubstituent, (f) an alkenylcarbonyloxy group optionally having asubstituent, (g) an alkynyloxy group optionally having a substituent,and (h) a hydroxy group.

The “alkoxy group” in the above “(a) an alkoxy group optionally having asubstituent” includes, for example, a linear or branched C₁₋₂₀ alkoxygroup. Preferred examples of the alkoxy group include a C₁₋₆ alkoxygroup. More preferred examples of the alkoxy group include a methoxygroup, an ethoxy group, a propoxy group, an isopropoxy group, a butoxygroup, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

The “aryloxy group” in the above “(b) an aryloxy group optionally havinga substituent” includes, for example, a C₅₋₁₀ monocyclic aryloxy groupand a C₈₋₁₂ bicyclic aryloxy group. Preferred examples of the aryloxygroup include a phenoxy group and a naphthyloxy group, and morepreferred examples thereof include a phenoxy group.

The “aralkyloxy group” in the above “(c) an aralkyloxy group optionallyhaving a substituent” includes, for example, a group in which an oxygroup is attached to the “aralkyl group” in the above “(5) an aralkylgroup optionally having a substituent”. Preferred examples of thearalkyloxy group include a benzyloxy group, a phenethyloxy group,1-naphthylmethoxy group, and 2-naphthylmethoxy group. More preferredexamples thereof include a benzyloxy group.

The above “(d) a silyloxy group optionally having a substituent” ispreferably, for example, a tert-butyldiphenylsiloxy group and atert-butyldimethylsiloxy group.

The “alkenyloxy group” in the above “(e) an alkenyloxy group optionallyhaving a substituent” includes, for example, a linear or branched C₂₋₂₀alkenyloxy group. Preferred examples of the alkenyloxy group include aC₂₋₆ alkenyloxy group. More preferred examples of the alkenyloxy groupinclude an ethenyloxy group, a 1-propenyloxy group, a 2-propenyloxygroup, a 1-methylethenyloxy group, a 1-butenyloxy group, a 2-butenyloxygroup, a 3-butenyloxy group, a 1-methyl-1-propenyloxy group, a1-methyl-2-propenyloxy group, a 2-methyl-1-propenyloxy group, and a2-methyl-2-propenyloxy group.

The “alkenylcarbonyloxy group” in the above “(f) an alkenylcarbonyloxygroup optionally having a substituent” includes, for example, a linearor branched C₂₋₂₀ alkenylcarbonyloxy group. Preferred examples of thealkenylcarbonyloxy group include a C₂₋₆ alkenylcarbonyloxy group. Morepreferred examples of the alkenylcarbonyloxy group include anethenylcarbonyloxy group, a 1-propenylcarbonyloxy group, a2-propenylcarbonyloxy group, a 1-methylethenylcarbonyloxy group, a1-butenylcarbonyloxy group, a 2-butenylcarbonyloxy group, a3-butenylcarbonyloxy group, a 1-methyl-1-propenylcarbonyloxy group, a1-methyl-2-propenylcarbonyloxy group, a 2-methyl-1-propenylcarbonyloxygroup, and a 2-methyl-2-propenylcarbonyloxy group.

The “alkynyloxy group” in the above “(g) an alkynyloxy group optionallyhaving a substituent” includes, for example, a linear or branched C₂₋₂₀alkynyloxy group. Preferred examples of the alkynyloxy group include aC₃₋₆ alkynyloxy group. More preferred examples of the alkynyloxy groupinclude a 2-propynyloxy group, a 1-methyl-2-propynyloxy group, a1,1-dimethyl-2-propynyloxy group, a 2-butynyloxy group, a 3-butynyloxygroup, a 1-pentynyloxy group, a 2-pentynyloxy group, a 3-pentynyloxygroup, and a 4-pentynyloxy group.

Examples of the “substituent” in the above (a) an alkoxy groupoptionally having a substituent, (b) an aryloxy group optionally havinga substituent, (c) an aralkyloxy group optionally having a substituent,(d) a silyloxy group optionally having a substituent, (e) an alkenyloxygroup optionally having a substituent, (f) an alkenylcarbonyloxy groupoptionally having a substituent, and (g) an alkynyloxy group optionallyhaving a substituent include the “substituent” in the above “(1) analkyl group optionally having a substituent”, “(2) a haloalkyl groupoptionally having a substituent”, “(3) an aryl group optionally having asubstituent”, “(4) a heteroaryl group optionally having a substituent”,“(5) an aralkyl group optionally having a substituent”, “(6) a silylgroup optionally having a substituent”, “(7) an alkenyl group optionallyhaving a substituent”, “(8) an alkynyl group optionally having asubstituent”, “(9) an acyl group optionally having a substituent”, and“(10) an alkenylcarbonyl group optionally having a substituent”.

Further preferred examples of the “substituted oxy group” of the presentinvention include a methoxy group, an oxiranylmethoxy group, anisopropoxy group, a hydroxybutoxy group, a 3-bromo-2-hydroxypropoxygroup, a benzyloxy group, a methoxybenzyloxy group, atert-butyldiphenylsiloxy group, a tert-butyldimethylsiloxy group, a2-methyl-2-propoxy group, a 1-methylethenylcarbonyloxy group, and ahydroxy group.

In the donor structure D of the chromophore of the present invention,the substituted oxy group may be attached to any of the ortho-, meta-,and para-carbon atoms of the aryl group, and the same or differentsubstituted oxy groups may be attached to the ortho-, meta-, or/andpara-carbon atoms of the aryl group. For example, preferred embodimentis that at least one substituted oxy group is attached to anortho-carbon atom of the aryl group, and more preferred embodiment isthat the substituted oxy group is attached to an ortho-carbon atom ofthe aryl group or to two or more of the ortho- and para-carbon atoms ofthe aryl group.

In the chromophore of the present invention, the substituted oxy groupin the donor structure D may form, together with the aryl carbon atom towhich the substituted oxy group is attached and with a carbon atom whichis adjacent to said carbon atom, a heterocyclic ring containing anoxygen atom as a hetero atom. The heterocyclic ring may have asubstituent. The heterocyclic ring includes, for example, a 5- to7-membered heterocyclic ring and may be an aliphatic ring or an aromaticring.

Preferably, in the chromophore of the present invention, the aryl groupin the donor structure D is further substituted with an amino groupoptionally having a substituent.

Examples of the “substituent” in the above “amino group optionallyhaving a substituent” include (α) an alkyl group, (β) a haloalkyl group,(γ) a hydroxyalkyl group, (δ) an acyloxyalkyl group, (ε) a silyloxyalkylgroup, (ζ) an aminoalkyl group, and (η) an aryl group. The mode ofsubstitution in the amino group with the substituent may bemono-substitution or di-substitution, but preferred is di-substitution.

Examples of the “(α) alkyl group” as the “substituent” in the above“amino group optionally having a substituent” include the “alkyl group”in the above “(1) an alkyl group optionally having a substituent”.Preferred examples of the (α) alkyl group include a C₁₋₆ alkyl group,and more preferred examples thereof include a methyl group, an ethylgroup, a propyl group, an isopropyl group, a butyl group, an isobutylgroup, a sec-butyl group, and a tert-butyl group.

Examples of the “(β) haloalkyl group” as the “substituent” in the above“amino group optionally having a substituent” include the “haloalkylgroup” in the above “(2) a haloalkyl group optionally having asubstituent”.

Examples of the “(γ) hydroxyalkyl group” as the “substituent” in theabove “amino group optionally having a substituent” include a linear orbranched C₁₋₂₀ alkyl group substituted with at least one hydroxy group.Examples of the hydroxyalkyl group include a hydroxy C₁₋₆ alkyl groupsuch as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropylgroup, and a hydroxybutyl group.

Examples of the “(δ) acyloxyalkyl group” as the “substituent” in theabove “amino group optionally having a substituent” include a linear orbranched C₁₋₂₀ alkyl group substituted with at least one acyloxy groupwhich may be the same as or different from each other.

Examples of the “(ε) silyloxyalkyl group” as the “substituent” in theabove “amino group optionally having a substituent” include a linear orbranched C₁₋₂₀ alkyl group substituted with at least one silyloxy group.

Examples of the “(ζ)aminoalkyl group” as the “substituent” in the above“amino group optionally having a substituent” include a linear orbranched C₁₋₂₀ alkyl group substituted with at least one amino group.

Examples of the “(η) aryl group” as the “substituent” in the above“amino group optionally having a substituent” include the “aryl group”in the above substituted oxyaryl, and preferred examples of the (η) arylgroup include a phenyl group and a naphthyl group.

When the above amino group has a substituent, the substituent may form,together with the nitrogen atom to which the substituent is attached, aheterocyclic ring containing the nitrogen atom as a hetero atom. Theheterocyclic ring may have a substituent. The heterocyclic ringincludes, for example, a 5- to 7-membered heterocyclic ring and may bean aliphatic ring or an aromatic ring.

When the above amino group has a substituent, the amino group also mayform, together with the aryl carbon atom to which the amino group isattached, a heterocyclic ring containing the nitrogen atom as a heteroatom. The heterocyclic ring may have a substituent. The heterocyclicring includes, for example, a 5- to 7-membered heterocyclic ring and maybe an aliphatic ring or an aromatic ring. When the amino group isdi-substituted, each substituent may form a heterocyclic ring containingthe nitrogen atom as a hetero atom.

Preferred donor structure D in the chromophore of the present inventionwill be illustrated below.

A preferred specific embodiment of the donor structure D is, forexample, a structure represented by the formula D-1:

wherein

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ² and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent); and

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a saturated heterocyclic ring optionally having asubstituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent.

The phrase “at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independentlyrepresents an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group” as used herein means that (1) anyone of R_(D) ¹, R_(D) ², and R_(D) ³ represents an alkoxy group, anaryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxygroup, an alkenylcarbonyloxy group, an alkynyloxy group, or a hydroxygroup; (2) two of R_(D) ¹, R_(D) ², and R_(D) ³ independently representan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; or (3) all of R_(D) ¹, R_(D) ², and R_(D) ³independently represent an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group.

The phrase “the rest independently represent a hydrogen atom or an alkylgroup” means that R_(D) ¹, R_(D) ², or/and R_(D) ³ not representing analkoxy group, an aryloxy group, an aralkyloxy group, a silyloxy group,an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group,or a hydroxy group independently represent a hydrogen atom or an alkylgroup.

In the present invention, the “alkoxy group”, “aryloxy group”,“aralkyloxy group”, “silyloxy group”, “alkenyloxy group”,“alkenylcarbonyloxy group”, and “alkynyloxy group” that R_(D) ¹, R_(D) ²and R_(D) ³ represent are, for example, the “alkoxy group” in the above“(a) an alkoxy group optionally having a substituent”, the “aryloxygroup” in the above “(b) an aryloxy group optionally having asubstituent”, the “aralkyloxy group” in the above “(c) an aralkyloxygroup optionally having a substituent”, the “silyloxy group” in theabove “(d) a silyloxy group optionally having a substituent”, the“alkenyloxy group” in the above “(e) an alkenyloxy group optionallyhaving a substituent”, the “alkenylcarbonyloxy group” in the above “(f)an alkenylcarbonyloxy group optionally having a substituent”, and the“alkynyloxy group” in the above “(g) an alkynyloxy group optionallyhaving a substituent”, respectively, as the above “substituted oxygroup”.

The “alkyl group” that R_(D) ¹, R_(D) ², and R_(D) ³ represent in thepresent invention includes, for example, the “alkyl group” in theabove“(1) an alkyl group optionally having a substituent”.

The phrase “R_(D) ¹, R_(D) ², and R_(D) ³ each may have the same ordifferent substituents” as used herein means that R_(D) ¹, R_(D) ², andR_(D) ³ may be independently substituted with one or more substituentswhich may be the same as or different from each other. Examples of thesubstituent include the “substituent” in the above “(1) an alkyl groupoptionally having a substituent”, “(2) a haloalkyl group optionallyhaving a substituent”, “(3) an aryl group optionally having asubstituent”, “(4) a heteroaryl group optionally having a substituent”,“(5) an aralkyl group optionally having a substituent”, “(6) a silylgroup optionally having a substituent”, “(7) an alkenyl group optionallyhaving a substituent”, “(8) an alkynyl group optionally having asubstituent”, “(9) an acyl group optionally having a substituent”, and“(10) an alkenylcarbonyl group optionally having a substituent”.

In the present invention, when R_(D) ² and R_(D) ³ are each attached toadjacent carbon atoms of the aryl of the donor structure D, R_(D) ² andR_(D) ³ may form, together with the two adjacent carbon atoms, a ringoptionally having a substituent. In this case, R_(D) ¹ represents analkoxy group optionally having a substituent, an aryloxy groupoptionally having a substituent, an aralkyloxy group optionally having asubstituent, a silyloxy group optionally having a substituent, analkenyloxy group optionally having a substituent, an alkenylcarbonyloxygroup optionally having a substituent, an alkynyloxy group optionallyhaving a substituent, or a hydroxy group. The ring that is formed byR_(D) ² and R_(D) ³ together with the two adjacent carbon atoms andoptionally has a substituent may be an aliphatic or aromatic carbocyclicring, and may be an aliphatic or aromatic heterocyclic ring. Forexample, the donor structure D represented by the following formula:

or the like(wherein

R represents an alkyl group, an aryl group, an aralkyl group, a silylgroup, an alkenyl group, an alkenylcarbonyl group, an alkynyl group, ora hydrogen atom, and R may have a substituent; and

R_(D) ⁴ and R_(D) ⁵ have the same meanings as defined for the aboveformula D-1)

is within the scope of the present invention.

In the present invention, when R_(D) ² and R_(D) ³ are each attached toadjacent carbon atoms of the aryl of the donor structure D, R_(D) ² andR_(D) ³ may form, together with the two adjacent carbon atoms, aheterocyclic ring containing an oxygen atom as a hetero atom. Forexample, the donor structure D represented by the following formula:

or the like(wherein

R represents an alkyl group, an aryl group, an aralkyl group, a silylgroup, an alkenyl group, an alkenylcarbonyl group, an alkynyl group, ora hydrogen atom, and R may have a substituent; and

R_(D) ⁴ and R_(D) ⁵ have the same meanings as defined for the aboveformula D-1)

is within the scope of the present invention.

The “alkyl group”, “haloalkyl group”, “hydroxyalkyl group”,“acyloxyalkyl group”, “silyloxyalkyl group”, “aminoalkyl group”, or“aryl group” that R_(D) ⁴ and R_(D) ⁵ represent are, for example, the(α) alkyl group, the (β) haloalkyl group, the (γ) hydroxyalkyl group,the (δ) acyloxyalkyl group, the (ε) silyloxyalkyl group, the (ζ)aminoalkyl group, and (η) the aryl group in the above “amino groupoptionally having a substituent”, respectively.

In the present invention, R_(D) ⁴ and R_(D) ⁵ may form, together withthe nitrogen atom to which they are attached, a heterocyclic ringoptionally having a substituent. The heterocyclic ring may have asubstituent. The heterocyclic ring includes, for example, a 5- to7-membered heterocyclic ring and may be an aliphatic ring or an aromaticring.

In the present invention, (a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D)³ and —NR_(D) ⁴R_(D) ⁵ may independently form, together with the carbonatoms to which they are attached, a heterocyclic ring containing thenitrogen atom as a hetero atom. The heterocyclic ring may have asubstituent. The heterocyclic ring includes, for example, a 5- to7-membered heterocyclic ring and may be an aliphatic ring or an aromaticring. For example, the donor structure D represented by the followingformula:

or the like(wherein

R_(D) ¹, R_(D) ⁴ and R_(D) ⁵ have the same meanings as defined for theabove formula D-1)

is within the scope of the present invention.

A more preferred specific embodiment of the donor structure D is, forexample, a structure represented by the formula D-1-1:

wherein

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent;

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ² and R_(D) ³ each mayhave the same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent); and

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a saturated heterocyclic ring optionally having asubstituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent.

Another more preferred specific embodiment of the donor structure D is,for example, a structure represented by the formula D-1-2:

wherein

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ² and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent); and

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a saturated heterocyclic ring optionally having asubstituent, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, with the aryl carbon atom to which said nitrogen atom isattached, and with the aryl carbon atom which is adjacent to said carbonatom, a heterocyclic ring containing the nitrogen atom as a hetero atomand optionally having a substituent.

In the present invention, when “R_(D) ⁴ and R_(D) ⁵ form, together withthe nitrogen atom to which they are attached, with the aryl carbon atomto which said nitrogen atom is attached, and with the aryl carbon atomwhich is adjacent to said carbon atom, a heterocyclic ring containingthe nitrogen atom as a hetero atom and optionally having a substituent”,the donor structure D may be, for example, a structure represented bythe following formula:

wherein

R_(D) ¹, R_(D) ², and R_(D) ³ have the same meanings as defined for theabove formula D-1-2; and

R represents a substituent.

Another preferred specific embodiment of the donor structure D is, forexample, a structure represented by the formula D-2:

wherein

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent).

A more preferred specific embodiment of the donor structure D is, forexample, a structure represented by the formula D-2-1:

wherein

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent; and

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ² and R_(D) ³ each mayhave the same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent).

In the above preferred specific embodiments of the donor structure D, afurther preferred embodiment is that, for example, at least one of R_(D)¹, R_(D) ², and R_(D) ³ represents a C₁₋₆ alkoxy group (for example, amethoxy group, an ethoxy group, a propoxy group, an isopropoxy group, abutoxy group, or the like), a benzyloxy group, atert-butyldiphenylsiloxy group, a tert-butyldimethylsiloxy group, or aC₂₋₆ alkenyloxy group (for example, a 2-methyl-2-propenyl group, or thelike); the rest represent a hydrogen atom; and R_(D) ¹, R_(D) ², andR_(D) ³ each may have the same or different substituents (for example, amethoxy group, a hydroxy group, an oxiranyl group, a bromine atom, orthe like).

In the above preferred specific embodiments of the donor structure D,another further preferred embodiment is that, for example, R_(D) ⁴ andR_(D) ⁵ each independently represent an alkyl group (for example, a C₁₋₆alkyl group such as a methyl group, an ethyl group, a propyl group, abutyl group, or the like), a hydroxyalkyl group (for example, a hydroxyC₁₋₆ alkyl group such as a hydroxymethyl group, a hydroxyethyl group, ahydroxypropyl group, a hydroxybutyl group, or the like), or asilyloxyalkyl group, and R_(D) ⁴ and R_(D) ⁵ each may have the same ordifferent substituents.

Acceptor Structure A

The acceptor structure A of the present invention is not particularlylimited as long as it is an electron acceptor group that is free of—SO₂—.

Preferred specific embodiments of the acceptor structure A include, forexample, structures represented by the following formulae:

wherein

Y represents —CR_(A) ¹R_(A) ²—, —O—, —S—, —SO—, —SiR_(A) ¹R_(A) ²—, —NR—(wherein R represents a hydrogen atom or an alkyl group) or —C(═CH₂)—;and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, analkoxy group, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A)² each may have the same or different substituents, or

R_(A) ¹ and R_(A) ² form, together with the carbon atom to which theyare attached, a structure that may have a substituent and is representedby the following formula:

The “alkyl group” that R_(A) ¹ and R_(A) ² represent includes, forexample, the “alkyl group” in the above “(1) an alkyl group optionallyhaving a substituent”. Preferred examples of the alkyl group include amethyl group and an isopropyl group.

The “alkenyl group” that R_(A) ¹ and R_(A) ² represent includes, forexample, the “alkenyl group” in the above “(7) an alkenyl groupoptionally having a substituent”.

The “cycloalkyl group” that R_(A) ¹ and R_(A) ² represent includes, forexample, a C₃₋₁₅ monocyclic or polycyclic saturated aliphatic ringgroup. Examples of the cycloalkyl group include a cyclopropyl group, acyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptylgroup, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, acyclounaecyl group, and a cyclododecyl group, and preferred examplesthereof include a cyclohexyl group.

The “cycloalkenyl group” that R_(A) ¹ and R_(A) ² represent includes,for example, a C₃₋₁₅ monocyclic or polycyclic unsaturated aliphatic ringgroup. Examples of the cycloalkenyl group include a cyclopropenyl group,a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, acyclooctenyl group, a cyclopentadienyl group, a cyclohexadienyl group, acycloheptadienyl group, and a cyclooctadienyl group.

The “alkoxy group” that R_(A) ¹ and R_(A) ² represent includes, forexample, the “alkoxy group” in the above “(a) an alkoxy group optionallyhaving a substituent”. Examples of the alkoxy group include a methoxygroup, an ethoxy group, a propoxy group, an isopropoxy group, a butoxygroup, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group.

The “haloalkyl group” that R_(A) ¹ and R_(A) ² represent includes, forexample, the “haloalkyl group” in the above “(2) a haloalkyl groupoptionally having a substituent”. Examples of the haloalkyl groupinclude a fluoromethyl group, a difluoromethyl group, a trifluoromethylgroup, a 2-fluoroethyl group, a 1,2-difluoroethyl group, a chloromethylgroup, a 2-chloroethyl group, a 1,2-dichloroethyl group, a bromomethylgroup, and an iodomethyl group, and more preferred examples thereofinclude a trifluoromethyl group.

The “aryl group” that R_(A) ¹ and R_(A) ² represent includes, forexample, a phenyl group and a naphthyl group, and preferred examplesthereof include a phenyl group.

Other preferred specific embodiments of the acceptor structure Ainclude, for example, structures represented by the following formulae:

More preferred specific embodiments of the acceptor structure A include,for example,

a structure represented by the formula A-a:

(wherein

Y represents —CR_(A) ¹R_(A) ²—, —O—, —S—, —SO—, —SiR_(A) ¹R_(A) ²—, —NR—(wherein R represents a hydrogen atom or an alkyl group), or —C(═CH₂)—;and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, analkoxy group, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A)² each may have the same or different substituents); and

a structure represented by the formula A-b:

(wherein

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, analkoxy group, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A)² each may have the same or different substituents).

Further preferred specific embodiments of the acceptor structure Ainclude, for example,

a structure represented by the formula A-a-1:

wherein

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents.

In the above specific embodiments of the acceptor structure A of thechromophore of the present invention, R_(A) ¹ and R_(A) ² may form,together with the carbon atom to which they are attached, a structurethat may have a substituent and is represented by the following formula:

That is, the acceptor structure A of the chromophore of the presentinvention also includes, for example, a structure represented by thefollowing formula:

or the like,wherein

Y represents —CR_(A) ¹R_(A) ²—, —O—, —S—, —SO—, —SiR_(A) ¹R_(A) ²—, —NR—(wherein R represents a hydrogen atom or an alkyl group), or —C(═CH₂)—.

π-Conjugated Bridge Structure B

The π-conjugated bridge structure B of the present invention is notparticularly limited as long as it has a conjugated system having aconjugated multiple bond and π-electrons are delocalized from the donorstructure D to the acceptor structure A through the electron orbitals ofthe bridge (cross-link).

The conjugated multiple bond in the π-conjugated bridge structure B maybe either of a double bond or a triple bond, and preferred is a doublebond. Examples of the π-conjugation include a carbon-carbon conjugationand a conjugation involving nitrogen. A preferred conjugation in thechromophore of the present invention is a carbon-carbon conjugation orthe like.

Preferred embodiments of the π-conjugated bridge structure B include,for example, structures represented by the following formulae:

wherein

R_(B) ¹ to R_(B) ⁸ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryl group, an alkenyl group, a cycloalkylgroup, a cycloalkenyl group, a haloalkyl group, an aralkyl group, anaryloxy group, or an aralkyloxy group, and R_(B) ¹ to R_(B) ⁸ each mayhave the same or different substituents;

n represents an integer of 1 to 5; and

m and m′ independently represent an integer of 0 to 3.

The “alkyl group” that R_(B) ¹ to R_(B) ⁸ represent includes, forexample, the “alkyl group” in the above “(1) an alkyl group optionallyhaving a substituent”. Preferred examples of the alkyl group include amethyl group, an ethyl group, a propyl group, an isopropyl group, ann-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group,a pentyl group, an isopentyl group, a hexyl group, an isohexyl group,and a heptyl group.

The “alkoxy group” that R_(B) ¹ to R_(B) ⁸ represent includes, forexample, the “alkoxy group” in the above “(a) an alkoxy group optionallyhaving a substituent”. Examples of the alkoxy group include a methoxygroup, an ethoxy group, a propoxy group, an isopropoxy group, a butoxygroup, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group,and preferred examples thereof include a methoxy group.

The “aryl group” that R_(B) ¹ to R_(B) ⁸ represent includes, forexample, a phenyl group and a naphthyl group, and preferred examples ofthe aryl group include a phenyl group.

The “alkenyl group” that R_(B) ¹ to R_(B) ⁸ represent includes, forexample, a linear or branched C₂₋₂₀ alkenyl group. Examples of thealkenyl group include an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, and a hexenyl group.

The “cycloalkyl group” that R_(B) ¹ to R_(B) ⁸ represent includes, forexample, a C₃₋₁₅ monocyclic or polycyclic saturated aliphatic ringgroup. Examples of the cycloalkyl group include a cyclopropyl group, acyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptylgroup, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, acyclounaecyl group, and a cyclododecyl group, and preferred examplesthereof include a cyclohexyl group.

The “cycloalkenyl group” that R_(B) ¹ to R_(B) ⁸ represent includes, forexample, a C₃₋₁₅ monocyclic or polycyclic unsaturated aliphatic ringgroup. Examples of the cycloalkenyl group include a cyclopropenyl group,a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, acyclooctenyl group, a cyclopentadienyl group, a cyclohexadienyl group, acycloheptadienyl group, and a cyclooctadienyl group.

The “haloalkyl group” that R_(B) ¹ to R_(B) ⁸ represent includes, forexample, the “haloalkyl group” in the above “(2) a haloalkyl groupoptionally having a substituent”. Examples of the haloalkyl groupinclude a fluoromethyl group, a difluoromethyl group, a trifluoromethylgroup, a 2-fluoroethyl group, a 1,2-difluoroethyl group, a chloromethylgroup, a 2-chloroethyl group, a 1,2-dichloroethyl group, a bromomethylgroup, and an iodomethyl group, and preferred examples thereof include atrifluoromethyl group.

The “aralkyl group” that R_(B) ¹ to R_(B) ⁸ represent includes, forexample, the “aralkyl group” in the above “(5) an aralkyl groupoptionally having a substituent”. Examples of the aralkyl group includea benzyl group, a 1-phenylethyl group, a phenethyl group, a1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethylgroup, and a 2-naphthylethyl group, and preferred examples thereofinclude a benzyl group.

The “aryloxy group” that R_(B) ¹ to R_(B) ⁸ represent includes, forexample, the “aryloxy group” in the above “(b) an aryloxy groupoptionally having a substituent”. Examples of the aryloxy group includea phenoxy group and a naphthyloxy group, and preferred examples thereofinclude a phenoxy group.

The “aralkyloxy group” that R_(B) ¹ to R_(B) ⁸ represent includes, forexample, the “aralkyloxy group” in the above “(c) an aralkyloxy groupoptionally having a substituent”. Examples of the aralkyloxy groupinclude a benzyloxy group, a phenethyloxy group, a 1-naphthylmethoxygroup, a 2-naphthylmethoxy group, and preferred examples thereof includea benzyloxy group.

Other preferred embodiments of the π-conjugated bridge structure Binclude, for example, structures represented by the following formulae:

wherein

R_(B) ¹ and R_(B) ² independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryl group, an alkenyl group, a cycloalkylgroup, a cycloalkenyl group, a haloalkyl group, an aralkyl group, anaryloxy group, or an aralkyloxy group, and R_(B) ¹ and R_(B) ² each mayhave the same or different substituents;

R_(B) ⁹ and R_(B) ¹⁰ independently represent a hydrogen atom or a cyanogroup (—CN); and

m represents an integer of 0 to 3.

More preferred specific embodiments of the π-conjugated bridge structureB include, for example,

a structure represented by the formula B-I:

(wherein

π¹ and π² independently represent the same or different carbon-carbonconjugated π-bonds, and π¹ and π² each may have the same or differentsubstituents; and

R_(B) ¹ and R_(B) ² independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryl group, an alkenyl group, a cycloalkylgroup, a cycloalkenyl group, a haloalkyl group, an aralkyl group, anaryloxy group, or an aralkyloxy group, and R_(B) ¹ and R_(B) ² each mayhave the same or different substituents);

a structure represented by the formula B-II

(wherein

π¹ and π² independently represent the same or different carbon-carbonconjugated π-bonds, and π¹ and π² each may have the same or differentsubstituents; and

R_(B) ¹, R_(B) ², R_(B) ³, and R_(B) ⁴ independently represent ahydrogen atom, an alkyl group, an alkoxy group, an aryl group, analkenyl group, a cycloalkyl group, a cycloalkenyl group, a haloalkylgroup, an aralkyl group, an aryloxy group, or an aralkyloxy group, andR_(B) ¹, R_(B) ², R_(B) ³, and R_(B) ⁴ each may have the same ordifferent substituents);

a structure represented by the formula B-III:

(wherein

m and m′ independently represent an integer of 0 to 3; and

R_(B) ¹, R_(B) ², and R_(B) ³ independently represent a hydrogen atom,an alkyl group, an alkoxy group, an aryl group, an alkenyl group, acycloalkyl group, a cycloalkenyl group, a haloalkyl group, an aralkylgroup, an aryloxy group, or an aralkyloxy group, and R_(B) ², and R_(B)³ each may have the same or different substituents); and

a structure represented by the formula B-IV:

(wherein

n represents an integer of 1 to 5).

Preferably, “the same or different carbon-carbon conjugated π-bonds” inthe present invention are, for example, structures represented by thefollowing formulae:

more preferably a structure represented by the following formula:

Preferred Specific Embodiments of Chromophore of the Present Invention

The chromophore of the present invention is represented by, for example,the formula D-B-A, wherein D represents the donor structure D, Brepresents the π-conjugated bridge structure B, and A represents theacceptor structure A.

Preferred specific embodiments of the chromophore of the presentinvention include, for example,

a compound represented by the formula I-1:

(wherein

π¹ and π² independently represent the same or different carbon-carbonconjugated π-bonds, and π¹ and π² each may have the same or differentsubstituents;

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

R_(B) ¹ and R_(B) ² independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryl group, an aralkyl group, an aryloxygroup, or an aralkyloxy group, and R_(B) ¹ and R_(B) ² each may have thesame or different substituents; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents);

a compound represented by the formula I-1-a:

(wherein

m and m′ independently, represents an integer of 0 to 3; and

R_(D) ¹ to R_(D) ⁵, R_(B) ², R_(A) ¹, and R_(A) ² have the same meaningsas defined for the above compound represented by the formula I-1);

a compound represented by the formula I-1-b:

(wherein

R_(D) ¹ to R_(D) ⁵, R_(B) ¹, R_(B) ², R_(A) ¹, and R_(A) ² have the samemeanings as defined for the above compound represented by the formulaI-1); and

a compound represented by the formula I-2:

(wherein

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent); and

π¹, π², R_(B) ¹, R_(B) ², R_(A) ¹, and R_(A) ² have the same meanings asdefined for the above compound represented by the formula I-1).

More preferred specific embodiments of the chromophore of the presentinvention include, for example,

a compound represented by the formula I-1-1:

(wherein

π¹ and π² independently represent the same or different carbon-carbonconjugated π-bonds, and π¹ and π² each may have the same or differentsubstituents;

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent;

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ² and R_(D) ³ each mayhave the same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a saturated heterocyclic ring optionally having asubstituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

R_(B) ¹ and R_(B) ² independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryl group, an aralkyl group, an aryloxygroup, or an aralkyloxy group, and R_(B) ¹ and R_(B) ² each may have thesame or different substituents; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents);

a compound represented by the formula I-1-1-a:

(wherein

m and m′ independently represents an integer of 0 to 3; and

R_(D) ¹ to R_(D) ⁵, R_(B) ¹, R_(B) ², R_(A) ¹, and R_(A) ² have the samemeanings as defined for the above compound represented by the formulaI-1-1); and

a compound represented by the formula I-1-1-b:

(wherein

R_(D) ¹ to R_(D) ⁵, R_(B) ¹, R_(B) ², R_(A) ¹, and R_(A) ² have the samemeanings as defined for the above compound represented by the formulaI-1-1).

Other preferred specific embodiments of the chromophore of the presentinvention include, for example,

a compound represented by the formula II-1:

(wherein

π¹ and π² independently represent the same or different carbon-carbonconjugated π-bonds, and π¹ and π² each may have the same or differentsubstituents;

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

R_(B) ², R_(B) ³, and R₅ ⁴ independently represent a hydrogen atom, analkyl group, an alkoxy group, an aryl group, an aralkyl group, anaryloxy group, or an aralkyloxy group, and R_(B) ¹, R_(B) ², R_(B) ³,and R_(B) ⁴ each may have the same or different substituents; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents);

a compound represented by the formula II-1-a:

(wherein

m and m′ independently represent an integer of 0 to 3; and

R_(D) ¹ to R_(D) ⁵, R_(B) ¹ to R_(B) ⁴, R_(A) ¹, and R_(A) ² have thesame meanings as defined for the above compound represented by theformula II-1); and

a compound represented by the formula II-1-b:

(wherein

R_(D) ¹ to R_(D) ⁵, R_(B) ¹ to R_(B) ⁴, R_(A) ¹, and R_(A) ² have thesame meanings as defined for the above compound represented by theformula II-1).

More preferred specific embodiments of the chromophore of the presentinvention include, for example,

a compound represented by the formula II-1-1:

(wherein

π¹ and π² independently represent the same or different carbon-carbonconjugated π-bonds, and π¹ and π² each may have the same or differentsubstituents;

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent;

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ² and R_(D) ³ each mayhave the same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a saturated heterocyclic ring optionally having asubstituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

R_(B) ¹, R_(B) ², R_(B) ³, and R_(B) ⁴ independently represent ahydrogen atom, an alkyl group, an alkoxy group, an aryl group, anaralkyl group, an aryloxy group, or an aralkyloxy group, and R_(B) ¹,R_(B) ², R_(B) ³, and R_(B) ⁴ each may have the same or differentsubstituents; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents);

a compound represented by the formula II-1-1-a:

(wherein

m and m′ independently represent an integer of 0 to 3; and

R_(D) ¹ to R_(D)5, R_(B) ¹ to R_(B) ⁴, R_(A) ¹, and R_(A) ² have thesame meanings as defined for the above compound represented by theformula II-1-1); and

a compound represented by the formula II-1-1-b:

(wherein

R_(D) ¹ to R_(D) ⁵, R_(B) ¹ to R_(B) ⁴, R_(A) ¹, and R_(A) ² have thesame meanings as defined for the above compound represented by theformula II-1-1).

Other preferred specific embodiments of the chromophore of the presentinvention include, for example,

a compound represented by the formula III-1:

(wherein

m and m′ independently represent an integer of 0 to 3;

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, a silyloxygroup, an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxygroup, or a hydroxy group; the rest independently represent a hydrogenatom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may havethe same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

R_(B) ¹, R_(B) ², and R_(B) ³ independently represent a hydrogen atom,an alkyl group, an alkoxy group, an aryl group, an aralkyl group, anaryloxy group, or an aralkyloxy group, and R_(B) ¹, R_(B) ², and R_(B) ³each may have the same or different substituents; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents); and

a compound represented by the formula III-1-a:

(wherein

R_(D) ¹ to R_(D) ⁵, R_(B) ¹ to R_(B) ³, R_(A) ¹, and R_(A) ² have thesame meanings as defined for the above compound represented by theformula III-1).

More preferred specific embodiments of the chromophore of the presentinvention include, for example,

a compound represented by the formula III-1-1:

(wherein

m and m′ independently represent an integer of 0 to 3;

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, or a hydroxy group, and R_(D) ¹ may have the same or differentsubstituents;

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, or ahydroxy group, and R_(D) ² and R_(D) ³ each may have the same ordifferent substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent;

R_(B) ¹, R_(B) ², R_(B) ³, and R_(B) ⁴ independently represent ahydrogen atom, an alkyl group, an alkoxy group, an aryl group, anaralkyl group, an aryloxy group, or an aralkyloxy group, and R_(B) ¹,R_(B) ², R_(B) ³, and R_(B) ⁴ each may have the same or differentsubstituents; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents); and

a compound represented by the formula III-1-1-a:

(wherein

R_(D) ¹ to R_(D) ⁵, R_(B) ¹ to R_(B) ³, R_(A) ¹, and R_(A) ² have thesame meanings as defined for the above compound represented by theformula III-1-1).

Other preferred specific embodiments of the chromophore of the presentinvention include, for example,

a compound represented by the formula IV-1-a:

(wherein

n represents an integer of 1 to 5;

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent;

R_(D) ² and R_(D) ³ independently represent a hydrogen atom, an alkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ² and R_(D) ³ each mayhave the same or different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent);

R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or

R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to which theyare attached, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent; or

(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent; and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents);

a compound represented by the formula IV-1-b:

(wherein

n, R_(D) ¹ to R_(D) ⁵, R_(A) ¹, and R_(A) ² have the same meanings asdefined for the above compound represented by the formula IV-1-a);

a compound represented by the formula IV-2-a:

(wherein

n represents an integer of 1 to 5;

at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independently representsan alkoxy group, an aryloxy group, an aralkyloxy group, silyloxy group,an alkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group,or a hydroxy group; the rest independently represent a hydrogen atom oran alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may have the sameor different substituents

(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D,

(1) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a ring optionally having a substituent; and

R_(D) ¹ represents an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or

(2) R_(D) ² and R_(D) ³ may form, together with the two adjacent carbonatoms, a heterocyclic ring containing an oxygen atom as a hetero atomand optionally having a substituent); and

R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, an alkylgroup, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A) ² eachmay have the same or different substituents); and

a compound represented by the formula IV-2-b:

(wherein

n, R_(D) ¹ to R_(D) ³, R_(A) ¹, and R_(A) ² have the same meanings asdefined for the above compound represented by the formula IV-2-a).

Production Process for Chromophore of the Present Invention

The chromophore of the present invention can be produced by a methodknown per se. The chromophore of the present invention can be producedby various methods such as a method described in, for example, Ann.,580, 44 (1953); Angew. Chem., 92, 671 (1980); Chem. Ber., 95, 581(1962); Macromolecules, 2001, 34, 253; Chem. Mater., 2007, 19, 1154;Org. Synth., VI, 901 (1980); Chem. Mater., 2002, 14, 2393; J. Mater.Sci., 39, 2335 (2004); “Preparative Organic Chemistry”, John Wiley(1975), p. 217; J. Org. Chem., 42, 353 (1977); J. Org. Chem., 33, 3382(1968); Synthesis, 1981, 165; or the like, an appropriately improvedmethod thereof, a combination method thereof, and the methods describedin Examples below.

The chromophore of the present invention can be produced by, forexample, the production processes described below. However, theproduction process of the chromophore of the present invention is notlimited to these reaction examples.

Production Process A

Among the chromophores of the present invention, the chromophorerepresented by the formula I-1-b:

(wherein

R_(D) ¹ to R_(D) ⁵, R_(B) ², R_(A) ¹, and R_(A) ² have the same meaningsas defined for the above chromophore represented by the formula I-1-b)

can be produced by, for example, reacting a compound represented by theformula IV-I:

(wherein

R_(D) ¹ to R_(D) ⁵, R_(B) ¹, and R_(B) ² have the same meanings asdefined for the above chromophore represented by the formula I-1-b) witha compound represented by the formula V:

(wherein

R_(A) ¹ and R_(A) ² have the same meanings as defined for the abovechromophore represented by the formula I-1-b).

The reaction of the compound represented by the formula IV-I with thecompound represented by the formula V is usually performed in a polarsolvent. The polar solvent may be a protonic polar solvent, anon-protonic polar solvent, or a combined polar solvent thereof.Examples of the protonic polar solvent include water, methanol, ethanol,1-propanol, 2-propanol, 1-butanol, acetic acid, formic acid, and acombined solvent thereof. Examples of the non-protonic polar solventinclude tetrahydrofuran (THF), acetone, acetonitrile,N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), methylenechloride, chloroform, dioxane, N-methylpyrrolidone, and a combinedsolvent thereof.

The reaction temperature is usually, for example, about 0 to 150° C.,preferably, for example, about 20 to 80° C.

The reaction time depends on the reaction temperature, but usually, forexample, about 1 hour to about 3 days.

The reaction atmosphere is usually air or the like.

After the reaction, usual treatment is carried out and the obtainedcrude product is purified as necessary according to a usual method, andthus the compound represented by the formula I-1-b can be obtained.

A raw material represented by the formula IV-I:

(wherein

R_(D) ¹ to R_(D) ⁵, R_(B) ¹, and R_(B) ² have the same meanings asdefined for the above chromophore represented by the formula I-1-b) forproducing the compound represented by the formula I-1-b can be producedby, for example, the following methods.

The compound represented by the formula IV-I can be obtained by, forexample, reacting a compound represented by the formula VI:

(wherein

R_(D) ¹ to R_(D) ⁵ have the same meanings as defined for the abovechromophore represented by the formula I-1-b)

with a compound represented by the formula VII-I-1:

(wherein

R_(B) ¹ and R_(B) ² have the same meanings as defined for the abovechromophore represented by the formula I-1-b;

Ar represents an aryl group; and

X represents a halogen atom)

or with a compound represented by the formula VII-I-2:

(wherein

R_(B) ¹ and R_(B) ² have the same meanings as defined for the abovechromophore represented by the formula I-1-b; and

R represents an alkyl group)

in the presence of a base to give a compound represented by the formulaVIII-I-1:

(wherein

R_(B) ¹ and R_(B) ² have the same meanings as defined for the abovechromophore represented by the formula I-1-b),

reacting the obtained compound represented by the formula VIII-1-1 withan alkyllithium (for example, n-butyllithium) or the like in an organicsolvent (for example, tetrahydrofuran), and reacting the resultingcompound with N,N-dimethylformamide, N-formylpiperidine, or the like.

Alternatively, the compound represented by the formula IV-1 can also beobtained by, for example, reacting a compound represented by the formulaVI:

(wherein

R_(D) ¹ to R_(D) ⁵ have the same meanings as defined for the abovechromophore represented by the formula I-1-b)

with a compound represented by the formula VII-I-3:

(wherein

R_(B) ¹, R_(B) ², and R_(B) ³ have the same meanings as defined for theabove chromophore represented by the formula I-1-b;

Ar represents an aryl group;

X represents a halogen atom; and

Y represents a hydrogen atom or a protective group for a hydroxy group)

in the presence of a base to give a compound represented by the formulaVIII-I-2:

(wherein

R_(D) ¹ to R_(D) ⁵, R_(B) ¹, and R_(B) ² have the same meanings asdefined for the above chromophore represented by the formula I-1-b; and

Y represents a hydrogen atom or a protective group for a hydroxy group),and

subjecting the obtained compound represented by the formula VIII-1-2 tooxidation (when Y represents a protective group for a hydroxy group,deprotection of the protective group is performed before the oxidation).

The aryl group in the above “an aryl group optionally having asubstituent” that Ar represents includes, for example, a phenyl group.

The “halogen atom” that X represents includes, for example, a fluorineatom, a chlorine atom, a bromine atom, and an iodine atom.

The “protective group for a hydroxy group” that Y represents is notparticularly limited as long as it has a function as a protective group,and examples thereof include an alkyl group (for example, a methylgroup, an ethyl group, an isopropyl group, a tert-butyl group, and thelike), an alkylsilyl group (for example, a trimethylsilyl group, atert-butyldimethylsilyl group, and the like), an alkoxymethyl group (forexample, methoxymethyl group, a 2-methoxyethoxymethyl group, and thelike), a tetrahydropyranyl group, a trimethylsilylethoxymethyl group, anaralkyl group (for example, a benzyl group, a p-methoxybenzyl group, a2,3-dimethoxybenzyl group, an o-nitrobenzyl group, a p-nitrobenzylgroup, a trityl group, and the like), and an acyl group (for example, aformyl group, an acetyl group, and the like).

The deprotection method may be a method known per se. Deprotection canbe carried out according to a method described in literature, forexample, T. W. Greene, Protective Groups in Organic Synthesis, JohnWiley & Sons, 1981, or a similar method thereto.

Production Process B

Among the chromophores of the present invention, the chromophorerepresented by the formula II-1-b:

(wherein

R_(D) ¹ to R_(D) ⁵, R_(B) ¹ to R_(B) ⁴, R_(A) ¹, and R_(A) ² have thesame meanings as defined for the above chromophore represented by theformula II-1-b)

can be produced by, for example, reacting a compound represented by theformula IV-II:

(wherein

R_(D) ¹ to R_(D) ⁵ and R_(B) ¹ to R_(B) ⁴ have the same meanings asdefined for the above chromophore represented by the formula II-1-b)

with a compound represented by the formula V:

(wherein

R_(A) ¹ and R_(A) ² have the same meanings as defined for the abovechromophore represented by the formula II-1-b).

The reaction of the compound represented by the formula IV-II with thecompound represented by the formula V can be usually performed under thesame conditions as those in the reaction of the above compoundrepresented by the formula IV-I with the compound represented by theformula V.

After the reaction, usual treatment is carried out and the obtainedcrude product is purified as necessary according to a usual method, andthus the compound represented by the formula II-1-b can be obtained.

A raw material represented by the formula IV-II:

(wherein

R_(D) ¹ to R_(D) ⁵ and R_(B) ¹ to R_(B) ⁴ have the same meanings asdefined for the above chromophore represented by the formula II-1-b) forproducing the compound represented by the formula II-1-b can be producedby, for example, the following method.

The compound represented by the formula IV-II can be obtained by, forexample, reacting a compound represented by the formula VI:

(wherein

R_(D) ¹ to R_(D) ⁵ have the same meanings as defined for the abovechromophore represented by the formula II-1-b)

with a compound represented by the formula VII-II-1:

(wherein

R_(B) ¹ to R_(B) ⁴ have the same meanings as defined for the abovechromophore represented by the formula II-1-b;

Ar represents an aryl group;

X represents a halogen atom; and

Y represents a hydrogen atom or a protective group for a hydroxy group)

or with a compound represented by the formula VII-II-2:

(wherein

R_(B) ¹ to R_(B) ⁴ have the same meanings as defined for the abovechromophore represented by the formula II-1-b; and

R represents an alkyl group) in the presence of a base to give acompound represented by the formula VIII-II:

(wherein

R_(D) ¹ to R_(D) ⁵ and R₅ ¹ to R_(B) ⁴ have the same meanings as definedfor the above chromophore represented by the formula II-1-b; and

Y represents a hydrogen atom or a protective group for a hydroxy group),and

subjecting the obtained compound represented by the formula VIII-II tooxidation (when Y represents a protective group for a hydroxy group,deprotection of the protective group is performed before the oxidation).

Production Process C

Besides Production Process B described above, the chromophorerepresented by the formula II-1-b:

(wherein

R_(D) ¹ to R_(D) ⁵, R_(B) ¹ to R_(B) ⁴, R_(A) ¹, and R_(A) ² have thesame meanings as defined for the above chromophore represented by theformula II-1-b)

also can be produced by, for example, the following method.

The chromophore represented by the formula II-1-b can be produced by,for example, reacting a compound represented by the formula IX-1:

(wherein

R_(B) ¹ to R_(B) ⁴, R_(A) ¹, and R_(A) ² have the same meanings asdefined for the above chromophore represented by the formula II-1-b;

Ar represents an aryl group; and

X represents a halogen atom)

or a compound represented by the formula IX-2:

(wherein

R_(B) ¹ to R_(R) ¹, and R_(A) ² have the same meanings as defined forthe above chromophore represented by the formula II-1-b; and

R represents an alkyl group)

with a compound represented by the formula VI:

(wherein

R_(D) ¹ to R_(D) ⁵ have the same meanings as defined for the abovechromophore represented by the formula II-1-b)

in the presence of a base.

The reaction of the compound represented by the formula IX-1 or thecompound represented by the formula IX-2 with the compound representedby the formula VI is usually performed in a polar or non-polar solventin the presence of a base such as an alkali metal alkoxide, an alkalimetal hydride, n-butyllithium, and phenyllithium.

The reaction temperature is usually, for example, about −30 to 100° C.,preferably, for example, about −10 to 50° C.

The reaction time is usually, for example, several minutes to about 5hours and is determined as appropriate based on the reaction progressmonitored by thin-layer chromatography or the like.

Preferably, the reaction atmosphere is usually, for example, an inertgas such as nitrogen and argon with exclusion of moisture.

After the reaction, usual treatment is carried out and the obtainedcrude product is purified as necessary according to a usual method, andthus the compound represented by the formula II-1-b can be obtained.

A raw material represented by the formula IX-1:

(wherein

R_(B) ¹ to R_(B) ⁴, R_(A) ¹, and R_(A) ² have the same meanings asdefined for the above chromophore represented by the formula II-1-b;

Ar represents an aryl group; and

X represents a halogen atom)

for producing the compound represented by the formula II-1-b can beproduced by, for example, the following method.

The compound represented by the formula IX-1 or the compound representedby the formula IX-2 can be obtained by, for example, reacting a compoundrepresented by the formula V:

(wherein

R_(A) ¹ and R_(A) ² have the same meanings as defined for the abovechromophore represented by the formula II-1-b)

with a compound represented by the formula X:

(wherein

R_(B) ¹ to R_(B) ⁴ have the same meanings as defined for the abovechromophore represented by the formula II-1-b; and

Y represents a hydrogen atom or a protective group for a hydroxy group)

to give a compound represented by the formula XI:

(wherein

R_(B) ¹ to R_(B) ⁴, R_(A) ¹, and R_(A) ² have the same meanings asdefined for the above chromophore represented by the formula II-1-b; and

Y represents a hydrogen atom or a protective group for a hydroxy group),

subjecting the obtained compound represented by the formula XI tohalogenation (when Y represents a protective group for a hydroxy group,deprotection of the protective group is performed before thehalogenation) to give a compound represented by the formula XII:

(wherein

R_(B) ¹ to R_(B) ⁴, R_(A) ¹, and R_(A) ² have the same meanings asdefined for the above chromophore represented by the formula II-1-b; and

X represents a halogen atom), and

reacting the obtained compound represented by the formula XII with PAr₃(wherein Ar represents an aryl group) or P(OR)₃ (wherein R represents analkyl group).

Production Process D

Among the chromophores of the present invention, the chromophorerepresented by the formula III-1-a:

(wherein

R_(D) ¹ to R_(D) ⁵, R_(B) ¹ to R_(B) ⁴, R_(A) ¹, and R_(A) ² have thesame meanings as defined for the above chromophore represented by theformula III-1-a)

can be produced by, for example, reacting a compound represented by theformula

(wherein

R_(D) ¹ to R_(D) ⁵ and R_(B) ¹ to R_(B) ³ have the same meanings asdefined for the above chromophore represented by the formula III-1-a)with a compound represented by the formula V:

(wherein

R_(A) ¹ and R_(A) ² have the same meanings as defined for the abovechromophore represented by the formula III-1-a).

The above reaction of the compound represented by the formula IV-IIIwith the compound represented by the formula V is usually performed in apolar solvent.

The reaction temperature is usually, for example, about 0 to 150° C.,preferably, for example, about 20 to 80° C.

The reaction time depends on the reaction temperature, but usually, forexample, about 1 hour to about 3 days.

The reaction atmosphere is usually air or the like.

After the reaction, usual treatment is carried out and the obtainedcrude product is purified as necessary according to a usual method, andthus the compound represented by the formula III-1-a can be obtained.

A raw material represented by the formula

(wherein

R_(D) ¹ to R_(D) ⁵ and R_(B) ¹ to R_(B) ³ have the same meanings asdefined for the above chromophore represented by the formula III-1-a)for producing the compound represented by the formula III-1-a can beproduced by, for example, the following method.

The compound represented by the formula IV-III can be produced by, forexample, reacting a compound represented by the formula VI:

(wherein

R_(D) ¹ to R_(D) ⁵ have the same meanings as defined for the abovechromophore represented by the formula III-1-a)

with a compound represented by the formula XIII:

(wherein

R_(B) ¹ to R_(B) ³ have the same meanings as defined for the abovechromophore represented by the formula III-1-a)

to give a compound represented by the formula XIV:

(wherein

R_(D) ¹ to R_(D) ⁵ and R_(B) ¹ to R_(B) ³ have the same meanings asdefined for the above chromophore represented by the formula III-1-a),reacting the obtained compound represented by the formula XIV with analkylidene imine such as C₆H₁₁N═CHCH₂Li, and treating the resultingcompound with water.

The production process of the chromophore of the present invention hasbeen described above. In the step of constructing an alkene, a cis ortrans isomer can be stereoselectively obtained by selecting anappropriate reaction, but usually the alkene is mostly obtained as amixture of cis and trans isomers. In cases where a desired stereoisomeris required, this purpose can be achieved by using a method known perse, such as chromatography, fractional crystallization, distillation,and isomerization.

Nonlinear Optical Material and Nonlinear Optical Element of the PresentInvention

The nonlinear optical material and nonlinear optical element of thepresent invention can be produced according to a known method (forexample, methods described in Oh et al., IEEE Journal on Selected Topicsin Quantum Electronics, Vol. 7, No. 5, pp. 826-835, September/October2001; Dalton et al., Journal of Materials Chemistry, 1999, 9, pp.1905-1920; Kaino, Denshi Joho Tsushin Gakkai Ronbunshi (IEICETRANSACTIONS on Electronics), C Vol. J84-C, No. 9, pp. 744-755,September, 2001; Ma et al., Advanced Materials, 2002, 14, No. 19, 2002,pp. 1339-1365; and the like).

The nonlinear optical material of the present invention comprises thechromophore of the present invention and a host material in which thechromophore is dispersed. Preferably, the chromophore of the presentinvention at a high concentration is uniformly dispersed in the hostmaterial so that the nonlinear optical material of the present inventioncan achieve excellent nonlinearly. For this purpose, the host materialpreferably has high compatibility with the chromophore of the presentinvention.

Examples of the host material include resins such as polymethacrylate(e.g., polymethylmethacrylate (PMMA)), polyimide, polycarbonate,polystyrene, polysulfone, polyethersulfone, a silicone resin, and anepoxy resin. These resins are preferred in that the resins are excellentin compatibility with the chromophore of the present invention and that,when the chromophore is used for a nonlinear optical element, the resinsare excellent in transparency and formability.

Dispersion of the chromophore of the present invention in the hostmaterial can be achieved by, for example, dissolving an appropriatemixing ratio of the chromophore and the host material in an organicsolvent, spin-coating a substrate with the mixture, and heating thesubstrate, and thus a thin film of the nonlinear optical material can beobtained.

The host material in the nonlinear optical material of the presentinvention preferably comprises a resin having a reactive functionalgroup capable of forming a covalent bond with the chromophore of thepresent invention. Further, at least part of the chromophore of thepresent invention is preferably attached to the resin having a reactivefunctional group. Such a nonlinear optical material in which thechromophore can be dispersed in the host material in a high density canachieve higher nonlinearly.

Examples of the above reactive functional group include a haloalkylgroup, a halogenated acyl group, an alkoxycarbonyl group, anaryloxycarbonyl group, a hydroxy group, an amino group, an isocyanategroup, an epoxy group, and a carboxy group. Such a reactive functionalgroup can react with a hydroxy group, an amino group, an alkoxycarbonylgroup, or the like contained in the chromophore of the presentinvention, thereby forming a covalent bond.

The nonlinear optical element of the present invention can be producedusing the nonlinear optical material of the present invention. Since thenonlinear optical material of the present invention is excellent innonlinearly and heat resistance, use of this material can give thenonlinear optical element an excellent optical performance and anexcellent durability for prolonged use.

FIG. 1 shows a schematic sectional view of an optical waveguideconstituting an arm of a Mach-Zehnder modulator, a specific embodimentof the nonlinear optical element of the present invention, but thepresent invention is not limited thereto.

In the optical waveguide 10 shown in FIG. 1, the following are stackedin the following order: a substrate 1, a lower electrode 2, a first cladlayer 3, a core layer 4, a second clad layer 6, and an upper electrode8. In the optical waveguide 10, the core layer 4 is formed with theabove nonlinear optical material that has been subjected to electricfield poling, and the optical waveguide core 9 formed by reactive ionetching or the like serves as a Mach-Zehnder interferometer. When anelectric field is applied from the lower electrode 2 and the upperelectrode 8, the refractive index of the core layer 4 positioned betweenthese electrodes varies, thereby changing the phase difference betweenboth arms of the Mach-Zehnder interferometer to modulate the intensityof a transmission light.

The first clad layer 3 and the second clad layer 6 are not particularlylimited as long as their refractive indexes are lower than that of thecore layer 4, and preferred examples thereof include ultraviolet curableor thermosetting resins, such as acrylic resins, epoxy resins, andsilicone resins; organic or inorganic composite sol-gel curablematerials such as polyimides and glass; silicon oxide; and the like. Thelower electrode 2 is, for example, a metal or a conductive film such asa conductive oxide film and a conductive organic polymer, and is used asan electrode during poling or during operation as an element. The upperelectrode 8 is an electrode for providing an input electric signal.

Although an example in which the optical waveguide 10 forms aMach-Zehnder modulator is illustrated herein, embodiments of thenonlinear optical element of the present invention are not limited toMach-Zehnder devices and may be other types of devices (for example,directional couplers or the like).

The applications of the nonlinear optical element of the presentinvention are not limited to optical modulators as long as theapplications involve the use of a film, optical waveguide, or the likemade of the chromophore or nonlinear optical material of the presentinvention. The nonlinear optical element of the present invention can beused for, besides optical modulators (e.g., for ultra high-speedtransmission, optical interconnection, optical signal processing, or thelike), for example, optical switches; optical memories; wavelengthconverters; electric field sensors for microwaves, millimeter waves,terahertz waves, or the like; biopotential sensors for musclepotentials, brain waves, or the like; spatial light modulators; opticalscanners; or the like, and further can be combined with electroniccircuits and used for optical signal transmission or the like betweenelectronic circuits.

EXAMPLES

The present invention will be illustrated below with reference toExamples, but the present invention is not limited thereto.

In the following Examples, the melting points were measured with a micromelting point apparatus (Yanagimoto Seisakusho) and the values were notcorrected. The nuclear magnetic resonance spectra (¹H-NMR and ¹³C-NMR)were measured with JNM-ECP600 (JEOL Ltd.) using, as solvent, CDCl₃,THF-d₈, or DMSO-d₆, and chemical shifts 5 from tetramethylsilane as theinternal standard were reported in ppm. The symbols used herein mean thefollowing: s: singlet, d: doublet, dd: double doublet, t: triplet, m:multiplet, b: broad, J: coupling constant.

Example 12-[4-2-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

(1-1) 4-dibutylamino-2-methoxybenzaldehyde

In 20 ml of 1-methyl-2-pyrrolidone were dissolved 2.49 g (9.9 mmol) of4-dibutylamino-2-hydroxybenzaldehyde and 3.5 g (24.6 mmol) of methyliodide. To this mixture was added 4.1 g (29.7 mmol) of anhydrouspotassium carbonate and the mixture was stirred with heating at 50° C.for 2 hours. After the reaction mixture was added to water, extractionwith ethyl acetate, washing with a saturated saline solution, dryingover anhydrous sodium sulfate, and concentration were performed. Theresidue was purified by silica gel column chromatography to give 2.58 gof a colorless oily matter (yield: 98.1%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.1 Hz), 1.35-1.41 (4H, m),1.59-1.63 (4H, m), 3.34 (4H, t, J=7.7 Hz), 3.88 (3H, s), 6.02 (1H, s),6.26 (1H, d, J=8.8 Hz), 7.69 (1H, d, J=8.8 Hz), 10.12 (1H, s)

(1-2) Dibutyl[3-methoxy-4-[2-(thiophene-2-yl)vinyl]phenyl]amine

In a stream of argon, to 20 ml of tetrahydrofuran was added 2.4 g ofphenyllithium (19% solution in dibutylether) (5.43 mmol), and 1.95 g(4.94 mmol) of 2-thenyl triphenylphosphonium chloride was added theretounder ice cooling. Next, 1.3 g (4.94 mmol) of4-dibutylamino-2-methoxybenzaldehyde was dissolved in tetrahydrofuranand added dropwise. The mixture was stirred under ice cooling for 1.5hours. After the reaction mixture was poured into water, extraction withethyl acetate, washing with a saturated saline solution, drying overanhydrous sodium sulfate, and concentration were performed. The residuewas purified by silica gel column chromatography to give 1.51 g of anorange oily matter (yield: 89.2%).

(1-3)5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-carboaldehyde

In a stream of argon, in 25 ml of tetrahydrofuran was dissolved 1.5 g(4.37 mmol) ofdibutyl[3-methoxy-4-[2-(thiophene-2-yl)vinyl]phenyl]amine, and 4.1 ml ofn-butyllithium (1.6 mol solution in hexane) (6.56 mmol) was addeddropwise thereto under cooling at −70 to −73° C. After the mixture wasstirred for 1 hour, 0.43 ml (5.54 mmol) of N,N-dimethylformamide wasadded dropwise. After the reaction mixture was stirred for 1 hour, thebath was removed and the temperature was allowed to rise. To thismixture, 10 ml of water was added dropwise. After the reaction mixturewas poured into water, extraction with ethyl acetate, washing with asaturated saline solution, drying over anhydrous sodium sulfate, andconcentration were performed. The residual liquid was dissolved in 200ml of ether and 70 mg of iodine pieces were added thereto. After stirredat room temperature, the mixture was washed with a 5% sodium bisulfitesolution and then with a saturated saline solution. After drying overanhydrous sodium sulfate and concentration were performed, the residuewas purified by silica gel column chromatography to give 1.27 g of areddish orange crystal (yield: 79.2%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.34-1.40 (4H, m),1.57-1.63 (4H, m), 3.31 (4H, t, J=7.7 Hz), 3.88 (3H, s), 6.12 (1H, d,J=2.2 Hz), 6.25 (1H, dd, J=2.2 Hz, 8.8 Hz), 7.02 (1H, d, J=3.8 Hz), 7.06(1H, d, J=15.9 Hz), 7.35 (1H, d, J=8.8 Hz), 7.41 (1H, d, J=15.9 Hz),7.61 (1H, d, J=3.8 Hz), 9.79 (1H, s)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.5, 50.9, 55.2, 94.4, 104.6,112.4, 116.0, 124.3, 128.7, 129.2, 137.7, 139.6, 150.1, 155.8, 159.1,182.2

(1-4)2-[4-[2-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 10 ml of ethanol and 3 ml of tetrahydrofuran were dissolved 300 mg(0.81 mmol) of5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-carboaldehyde and177 mg (0.89 mmol) of2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile. To thismixture was added 63 mg of ammonium acetate, and the mixture was stirredat room temperature for 24 hours and further at 50° C. for 2.5 hours.The solvent was evaporated off and the residue was washed with ethanolto give 335 mg of a brown powdered crystal (yield: 75.1%; mp: 191-192°C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.7 Hz), 1.35-1.41 (4H, m),1.59-1.64 (4H, m), 1.74 (6H, s), 3.33 (4H, t, J=7.7 Hz), 3.91 (3H, s),6.11 (1H, d, J=2.2 Hz), 6.28 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.53 (1H, d,J=15.4 Hz), 6.99 (1H, d, J=4.4 Hz), 7.08 (1H, d, J=15.9 Hz), 7.34 (1H,d, J=4.4 Hz), 7.37 (1H, d, J=8.8 Hz), 7.44 (1H, d, J=15.9 Hz), 7.75 (1H,d, J=15.4 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 26.6, 29.6, 50.9, 55.2, 55.3,94.2, 96.7, 104.9, 111.1, 111.3, 111.7, 112.4, 115.7, 126.5, 129.0,130.8, 137.0, 138.1, 139.4, 150.7, 156.6, 159.6, 172.8, 175.9

Example 22-[4-[2-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5-methyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 4 ml of ethanol and 1.5 ml of tetrahydrofuran were dissolved 100 mg(0.27 mmol) of5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-carboaldehyde and75 mg (0.3 mmol) of2-(3-cyano-4,5-dimethyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.After the mixture was stirred at 50° C. for 2 hours, the solvent wasevaporated off. The residue was washed with ethanol to give 120 mg of abrown powdered crystal (yield: 73.5%; mp: 191-193° C.)

¹H-NMR (600 MHz, DMSO-d₆) δ: 0.93 (6H, t, J=7.7 Hz), 1.31-1.37 (4H, m),1.52-1.57 (4H, m), 2.09 (3H, s), 3.38 (4H, t, J=7.7 Hz), 3.88 (3H, s),6.17 (1H, d, J=2.2 Hz), 6.35 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.65 (1H, d,J=14.8 Hz), 7.30 (1H, d, J=3.8 Hz), 7.34 (1H, d, J=15.9 Hz), 7.47 (1H,d, J=15.9 Hz), 7.50 (1H, d, J=8.8 Hz), 7.87 (1H, d, J=3.8 Hz), 8.22 (1H,d, J=14.8 Hz)

¹³C-NMR (150 MHz, DMSO-d₆) δ: 13.7, 17.9, 19.5, 29.1, 49.9, 54.3, 55.2,94.0, 94.7, 105.1, 110.2, 111.25, 111.34, 111.8, 112.0, 115.7, 120.8,128.3, 129.7, 131.6, 137.5, 141.1, 141.6, 150.9, 158.7, 159.5, 161.9,176.1

Example 32-[4-[2-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 8 ml of ethanol and 2.5 ml of tetrahydrofuran were dissolved 226 mg(0.61 mmol) of5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-carboaldehyde and210 mg (0.62 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.The mixture was stirred with heating at 70° C. for 4 hours. The solventwas evaporated off and the residue was washed with ethanol. The residuewas purified by silica gel column chromatography and washed with ethanolto give 378 mg of a dark brown powdered crystal (yield: 92.9%; mp:203-204° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.7 Hz), 1.35-1.41 (4H, m),1.59-1.64 (4H, m), 3.34 (4H, t, J=7.7 Hz), 3.90 (3H, s), 6.09 (1H, d,J=2.2 Hz), 6.27 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.56 (1H, d, J=15.4 Hz),6.99 (1H, d, J=4.4 Hz), 7.09 (1H, d, J=15.4 Hz), 7.29 (1H, d, J=4.4 Hz),7.37 (1H, d, J=8.8 Hz), 7.49 (1H, d, J=15.9 Hz), 7.51-7.56 (5H, m), 7.76(1H, d, J=15.9 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.6, 51.0, 55.2, 57.4, 94.0,105.2, 110.9, 111.1, 111.3, 111.4, 112.5, 115.7, 126.9, 127.3, 129.6,129.7, 129.9, 131.4, 132.6, 137.7, 140.2, 141.6, 151.2, 159.7, 160.1,161.7, 175.5

Example 42-[4-[2-[5-[2-(2-benzyloxy-4-dibutylaminophenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

(4-1) 2-benzyloxy-4-dibutylaminobenzaldehyde

In 20 ml of 1-methyl-2-pyrrolidone were dissolved 1.86 g (7.46 mmol) of4-dibutylamino-2-hydroxybenzaldehyde and 1.66 g (9.71 mmol) of benzylbromide. To this mixture was added 2.06 g (14.9 mmol) of anhydrouspotassium carbonate and the mixture was stirred with heating at 50° C.for 2 hours. After the reaction mixture was added to water, extractionwith ethyl acetate, washing with a saturated saline solution, dryingover anhydrous sodium sulfate, and concentration were performed. Theresidue was purified by silica gel column chromatography to give 2.31 gof a pale yellow crystal (yield: 91.3%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.94 (6H, t, J=7.1 Hz), 1.29-1.34 (4H, m),1.49-1.54 (4H, m), 3.27 (4H, t, J=7.1 Hz), 5.18 (2H, s), 6.02 (1H, s),6.26 (1H, d, J=8.8 Hz), 7.31 (1H, m), 7.37-7.40 (2H, m), 7.40-7.44 (2H,m), 7.72 (1H, d, J=8.8 Hz), 10.24 (1H, s)

(4-2) [3-benzyloxy-4-[2-(thiophene-2-yl)vinyl]phenyl]dibutylamine

In a stream of argon, to 25 ml of tetrahydrofuran was added 3.3 g ofphenyllithium (19% solution in dibutylether) (7.46 mmol), and 2.68 g(6.79 mmol) of 2-thenyl triphenylphosphonium chloride was added theretounder ice cooling. Next, 2.3 g (6.78 mmol) of2-benzyloxy-4-dibutylaminobenzaldehyde was dissolved in tetrahydrofuranand added dropwise. The mixture was stirred under ice cooling for 2hours. After the reaction mixture was poured into water, extraction withethyl acetate, washing with a saturated saline solution, drying overanhydrous sodium sulfate, and concentration were performed. To theresidue, 40 ml of ethyl acetate/hexane (4/1) was added and theprecipitate was filtered off. The filtrate was concentrated and thenpurified by silica gel column chromatography to give 2.64 g of a yellowoily matter (yield: 92.9%).

(4-3)5-[2-(2-benzyloxy-4-dibutylaminophenyl)vinyl]thiophene-2-carboaldehyde

In a stream of argon, in 35 ml of tetrahydrofuran was dissolved 2.6 g(6.2 mmol) of[3-benzyloxy-4-[2-(thiophene-2-yl)vinyl]phenyl]dibutylamine, and 5.8 mlof n-butyllithium (1.6 mol solution in hexane) (9.28 mmol) was addeddropwise thereto under cooling at −71 to −74° C. The mixture was stirredfor 1 hour. Next, 0.59 g (8.07 mmol) of N,N-dimethylformamide was addeddropwise. The reaction mixture was stirred for 1 hour and thetemperature was allowed to rise. To this mixture, 10 ml of water wasadded dropwise. After the reaction mixture was poured into water,extraction with ethyl acetate, washing with a saturated saline solution,drying over anhydrous sodium sulfate, and concentration were performed.The residual liquid was dissolved in 300 ml of ether and 130 mg ofiodine pieces were added thereto. After stirred at room temperature, themixture was washed with a 5% sodium bisulfite solution and then with asaturated saline solution. After drying over anhydrous magnesium sulfateand concentration, the residue was crystallized from ethylacetate/hexane (⅙) and the precipitate was separated by filtration togive 1.76 g of a reddish orange crystal. Further, the mother liquor waspurified by silica gel column chromatography and the residue wascrystallized in the same manner as described above to further give 0.12g of the crystal (In total: 1.88 g; yield: 67.8%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.94 (6H, t, J=7.7 Hz), 1.28-1.34 (4H, m),1.48-1.53 (4H, m), 3.23 (4H, t, J=7.7 Hz), 5.16 (2H, s), 6.12 (1H, d,J=2.2 Hz), 6.26 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.98 (1H, d, J=3.8 Hz), 7.11(1H, d, J=15.9 Hz), 7.32-7.48 (7H, m), 7.60 (1H, d, J=3.8 Hz), 9.79 (1H,s) ¹³C-NMR (150 MHz, CDCl₃) δ: 14.1, 20.4, 29.6, 51.0, 70.5, 96.5,105.0, 112.8, 116.0, 116.3, 127.1, 128.0, 128.8, 129.0, 129.4, 137.3,137.8, 139.8, 150.0, 155.8, 158.4, 182.3

(4-4) 2-[4-[2-[5-[2-(2-benzyloxy-4-dibutylaminophenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 10 ml of ethanol and 5 ml of tetrahydrofuran were dissolved 300 mg(0.67 mmol) of5-[2-(2-benzyloxy-4-dibutylaminophenyl)vinyl]thiophene-2-carboaldehydeand 147 mg (0.74 mmol) of2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile. To thismixture was added 52 mg of ammonium acetate, and the mixture was stirredat room temperature for 18 hours and further stirred with heating at 50°C. for 7 hours. The solvent was evaporated off and the residue waswashed with ethanol to give 246 mg of a dark brown crystal (yield:58.4%; mp: 218-219° C.)

¹H-NMR (600 MHz, DMSO-d₆) δ: 0.89 (6H, t, J=7.7 Hz), 1.25-1.311 (4H, m),1.40-1.45 (4H, m), 1.78 (6H, s), 3.27 (4H, t, J=7.7 Hz), 5.27 (2H, s),6.18 (1H, d, J=2.2 Hz), 6.29 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.63 (1H, d,J=15.4 Hz), 7.15 (1H, d, J=3.8 Hz), 7.30 (1H, d, J=15.9 Hz), 7.32-7.35(1H, m), 7.41-7.48 (5H, m), 7.43 (1H, d, J=15.9H), 7.73 (1H, d, J=3.8Hz), 8.09 (1H, d, J=15.4 Hz)

¹³C-NMR (150 MHz, DMSO-d₆) δ: 13.7, 19.5, 25.5, 29.0, 49.9, 52.3, 69.3,95.5, 96.0, 98.3, 104.9, 111.25, 111.33, 111.9, 112.3, 113.0, 115.9,126.9, 127.2, 127.6, 128.4, 129.1, 137.0, 137.3, 139.1, 140.2, 150.0,154.7, 157.9, 174.3, 176.8

Example 52-[4-[2-[5-[2-(2-benzyloxy-4-dibutylaminophenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5-methyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 10 ml of ethanol and 2 ml of tetrahydrofuran were dissolved 730 mg(1.63 mmol) of5-[2-(2-benzyloxy-4-dibutylaminophenyl)vinyl]thiophene-2-carboaldehydeand 380 mg (1.5 mmol) of2-(3-cyano-4,5-dimethyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.The mixture was stirred at room temperature for 19 hours and furtherstirred with heating at 50° C. for 6 hours. The solvent was evaporatedoff and the residue was washed with ethanol to give 860 mg of a darkreddish brown crystal (yield: 94.0%; mp: 184-185° C.)

¹H-NMR (600 MHz, CDCl₆) δ: 0.94 (6H, t, J=7.7 Hz), 1.28-1.35 (4H, m),1.49-1.54 (4H, m), 1.90 (3H, s), 3.26 (4H, t, J=7.7 Hz), 5.21 (2H, s),6.09 (1H, d, J=2.2 Hz), 6.28 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.43 (1H, d,J=15.4 Hz), 7.00 (1H, d, J=3.8 Hz), 7.17 (1H, d, J=15.9 Hz), 7.34-7.46(6H, m), 7.38 (1H, d, J=8.8 Hz), 7.56 (1H, d, J=15.9 Hz), 8.15 (1H, d,J=15.4 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 19.3, 20.3, 29.5, 51.0, 70.4, 96.1,105.4, 109.9, 110.8, 111.4, 112.8, 116.0, 122.4, 126.9, 127.4, 128.1,128.8, 129.9, 132.7, 136.9, 137.7, 140.2, 141.1, 151.0159.2, 159.4,161.7, 174.9, 175.5

Example 62-[4-[2-[5-[2-(2-benzyloxy-4-dibutylaminophenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 15 ml of ethanol and 5 ml of tetrahydrofuran were dissolved 730 mg(1.63 mmol) of5-[2-(2-benzyloxy-4-dibutylaminophenyl)vinyl]thiophene-2-carboaldehydeand 573 mg (1.82 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.The mixture was stirred at room temperature for 21 hours and furtherstirred with heating at 50° C. for 3 hours. The solvent was evaporatedoff and the residue was washed with ethanol to give 1.15 g of a darkreddish brown crystal (yield: 94.7%; mp: 196-197° C.)

¹H-NMR (600 MHz, CDCl₆) δ: 0.94 (6H, t, J=7.7 Hz), 1.28-1.34 (4H, m),1.48-1.53 (4H, m), 3.25 (4H, t, J=7.7 Hz), 5.20 (2H, s), 6.08 (1H, d,J=2.2 Hz), 6.27 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.55 (1H, d, J=15.4 Hz),6.93 (1H, d, J=3.8 Hz), 7.13 (1H, d, J=15.9 Hz), 7.28 (1H, d, J=3.8 Hz),7.33-7.45 (6H, m), 7.50-7.56 (6H, m), 7.79 (1H, d, J=15.4 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.3, 29.5, 51.0, 57.5, 70.4, 96.1,105.4, 110.9, 111.1, 111.2, 111.3, 112.8, 116.0, 126.8, 126.9, 127.3,128.1, 128.7, 129.7, 129.9, 131.4, 132.7, 136.9, 137.8, 140.1, 141.6,151.0, 159.2, 159.6, 161.7, 175.5

Example 72-[4-[2-[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]phenyl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

(7-1)Dibutyl[4-[2-[4-(tert-butyldiphenylsiloxymethyl)phenyl]vinyl]-3-methoxyphenyl]amine

In a stream of argon, to 35 ml of tetrahydrofuran was added 3.33 g ofphenyllithium (19% solution in dibutylether) (7.53 mmol), and 4.8 g(6.84 mmol) of4-(tert-butyldiphenylsiloxymethyl)benzyltriphenylphosphonium bromide wasadded thereto under ice cooling. Next, 1.8 g (6.838 mmol) of4-dibutylamino-2-methoxybenzaldehyde was dissolved in tetrahydrofuranand added dropwise. The mixture was stirred for 1.5 hours. After thereaction mixture was poured into water, extraction with ethyl acetate,washing with a saturated saline solution, drying over anhydrous sodiumsulfate, and concentration were performed. Ethyl acetate/hexane (5/1)was added to the residue and the precipitate was filtered off. Thefiltrate was reconcentrated and the residue was purified by silica gelcolumn chromatography to give 3.92 g of a yellow liquid (yield: 94.7%).

(7-2) [4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]phenyl]methanol

In 50 ml of tetrahydrofuran was dissolved 3.9 g (6.44 mmol) ofdibutyl[4-[2-[4-(tert-butyldiphenylsiloxymethyl)phenyl]vinyl]-3-methoxyphenyl]amine,and 20 ml of tetrabutylammonium fluoride (1 mol solution intetrahydrofuran) was added dropwise thereto with stirring at roomtemperature. The mixture was stirred for 2.5 hours. After the reactionmixture was poured into water, extraction with ethyl acetate, washingwith a saturated saline solution, drying over anhydrous sodium sulfate,and concentration were performed. The residue was purified by silica gelcolumn chromatography to give 2.28 g of a yellow liquid (yield: 96.4%).

(7-3) 4-[2-(4-dibutylamino-2-methoxyphenyl) vinyl]benzaldehyde

In 60 ml of dichloromethane was dissolved 2.28 g (6.2 mmol) of[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]phenyl]methanol, and 10.8 gof active manganese dioxide was added thereto. The mixture was stirredat room temperature for 18 hours. After the reaction mixture wasfiltrated and concentrated, the residue was dissolved in 170 ml ofether, 80 mg of iodine pieces were added thereto, and the mixture wasstirred. The reaction mixture was washed with a 5% sodium bisulfitesolution and then with a saturated saline solution, and dried overanhydrous magnesium sulfate. After ether was evaporated off, the residuewas purified by silica gel column chromatography to give 1.54 g of anorange oily matter (yield: 67.9%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.35-1.41 (4H, m),1.58-1.63 (4H, m), 3.31 (4H, t, J=7.7 Hz), 3.88 (3H, s), 6.15 (1H, d,J=2.2 Hz), 6.28 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.95 (1H, d, J=15.9 Hz),7.45 (1H, d, J=8.8 Hz), 7.56 (1H, d, J=15.9 Hz), 7.60 (2H, d, J=8.2 Hz),7.80 (2H, d, J=8.2 Hz), 9.94 (1H, s)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.4, 29.6, 50.9, 55.3, 94.6, 104.6,113.2, 122.3, 126.1, 127.6, 128.0, 130.2, 134.1, 145.6, 149.9, 158.8,191.7

(7-4)2-[4-[2-[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]phenyl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 15 ml of ethanol and 5 ml of tetrahydrofuran were dissolved 500 mg(1.37 mmol) of 4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]benzaldehydeand 300 mg (1.51 mmol) of 2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile. To this mixture was added 106 mg of ammonium acetate,and the mixture was stirred at room temperature for 23 hours. Thesolvent was evaporated off in a reduced pressure. The residue was washedwith ethanol and then purified by silica gel column chromatography. Thecrystal was washed with ethanol to give 693 mg of a black powder (yield:92.6%; mp: 258-260° C.) ¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.7Hz), 1.35-1.41 (4H, m), 1.59-1.64 (4H, m), 1.80 (6H, s), 3.33 (4H, t,J=7.7 Hz), 3.90 (3H, s), 6.14 (1H, d, J=2.2 Hz), 6.29 (1H, dd, J=2.2 Hz,8.8 Hz), 6.94 (1H, d, J=16.5 Hz), 6.98 (1H, d, J=15.9 Hz), 7.45 (1H, d,J=8.8 Hz), 7.54 (2H, d, J=8.8 Hz), 7.56 (2H, d, J=8.8 Hz), 7.58 (1H, d,J=15.9 Hz), 7.59 (1H, d, J=16.5 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.4, 26.6, 29.6, 50.9, 55.3, 57.0,94.4, 97.3, 98.4, 104.8, 110.6, 111.2, 111.9, 113.0, 122.0, 126.7,128.0, 128.2, 129.8, 131.3, 144.7, 147.3, 150.1, 159.0, 173.8, 175.5

Example 82-[4-[2-[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]phenyl]vinyl]-3-cyano-5-methyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 15 ml of ethanol and 5 ml of tetrahydrofuran were dissolved 500 mg(1.37 mmol) of 4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]benzaldehydeand 380 mg (1.50 mmol) of2-(3-cyano-4,5-dimethyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.The mixture was stirred at 50° C. for 9 hours. The solvent wasevaporated off and the residue was washed with ethanol. The residue waspurified by silica gel column chromatography and washed with ethanol togive 320 mg of a black powder (yield: 38.9%; mp: 175-177° C.)

¹H-NMR (600 MHz, CDCl₃) δ0.98 (6H, t, J=7.7 Hz), 1.35-1.42 (4H, m),1.59-1.64 (4H, m), 1.97 (3H, s), 3.33 (4H, t, J=7.7 Hz), 3.90 (3H, s),6.14 (1H, d, J=2.2 Hz), 6.29 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.91 (1H, d,J=15.9 Hz), 6.96 (1H, d, J=16.5 Hz), 7.46 (1H, d, J=8.8 Hz), 7.55 (2H,d, J=8.8 Hz), 7.58 (2H, d, J=8.8 Hz), 7.63 (1H, d, J=16.5 Hz), 8.00 (1H,d, J=15.9 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 19.2, 20.3, 29.6, 50.9, 55.3, 59.8,94.3, 99.3, 104.8, 110.0, 110.4, 110.6, 111.9, 113.0, 121.9, 126.8,128.4, 128.9, 130.5, 131.4, 145.8, 149.6, 150.3, 159.2, 163.3, 174.8,186.4

Example 92-[4-[2-[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]phenyl]vinyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 15 ml of ethanol and 5 ml of tetrahydrofuran were dissolved 540 mg(1.48 mmol) of 4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]benzaldehydeand 500 mg (1.59 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.The mixture was stirred at 50° C. for 4 hours. The solvent wasevaporated off and the residue was washed with ethanol. The residue waspurified by silica gel column chromatography and washed with ethanol togive 160 mg of a black powder (yield: 17.7%; mp: 176-178° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.35-1.41 (4H, m),1.58-1.63 (4H, m), 3.32 (4H, t, J=7.7 Hz), 3.89 (3H, s), 6.12 (1H, d,J=2.2 Hz), 6.27 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.92 (1H, d, J=15.9 Hz),7.00 (1H, d, J=15.9 Hz), 7.43-7.59 (10H, m), 7.59 (1H, d, J=15.9 Hz),7.66 (1H, d, J=15.9 Hz) ¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.6,50.9, 55.3, 60.0, 94.3, 99.9, 104.8, 110.1, 110.3, 110.6, 112.9, 113.1,121.9, 126.7, 126.9, 128.4, 128.9, 129.3, 129.9, 130.5, 131.4, 131.7,145.8, 150.3, 150.4, 159.2, 163.5, 175.0

Example 102-[4-[2-[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2,5-dimethylphenyl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

(10-1)Dibutyl[4-[2-[4-(tert-butyldiphenylsiloxymethyl)-2,5-dimethylphenyl]vinyl]-3-methoxyphenyl]amine

In a stream of argon, to 20 ml of tetrahydrofuran was added 2.54 g ofphenyllithium (19% solution in dibutylether) (5.74 mmol), and 3.57 g(4.89 mmol) of4-(tert-butyldiphenylsiloxymethyl)-2,5-dimethylbenzyltriphenylphosphoniumbromide was added thereto under ice cooling. Next, 1.26 g (4.78 mmol) of4-dibutylamino-2-methoxybenzaldehyde was dissolved in tetrahydrofuranand added dropwise. The mixture was stirred for 1.5 hours. After thereaction mixture was poured into water, extraction with ethyl acetate,washing with a saturated saline solution, drying over anhydrous sodiumsulfate, and concentration were performed. The residue was purified bysilica gel column chromatography to give 2.7 g of an orange liquid(yield: 89.1%).

(10-2)[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2,5-dimethylphenyl]methanol

In 30 ml of tetrahydrofuran was dissolved 2.7 g (4.26 mmol) ofdibutyl[4-[2-[4-(tert-butyldiphenylsiloxymethyl)-2,5-dimethylphenyl]vinyl]-3-methoxyphenyl]amine,and 13.0 ml of tetrabutylammonium fluoride (1 mol solution intetrahydrofuran) was added dropwise thereto with stirring at roomtemperature. The mixture was stirred for 3 hours. After the reactionmixture was poured into water, extraction with ethyl acetate, washingwith a saturated saline solution, drying over anhydrous sodium sulfate,and concentration were performed. The residue was purified by silica gelcolumn chromatography to give 1.57 g of a yellow liquid (yield: 93.5%).

(10-3)4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2,5-dimethylbenzaldehyde

In 50 ml of dichloromethane was dissolved 1.5 g (3.79 mmol) of[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2,5-dimethylphenyl]methanol,and 6.6 g of active manganese dioxide was added thereto. The mixture wasstirred at room temperature for 21 hours. After the reaction mixture wasfiltrated and concentrated, the residue was dissolved in 50 ml of ether.60 mg of iodine pieces were added thereto, and the reaction mixture wasstirred. The reaction mixture was washed with a 5% sodium bisulfitesolution and then with a saturated saline solution, and dried overanhydrous magnesium sulfate. After ether was evaporated off, the residuewas purified by silica gel column chromatography to give 1.09 g of areddish orange crystal (yield: 72.4%).

¹H-NMR (600 MHz, CDCl₃) S: 0.97 (6H, t, J=7.7 Hz), 1.35-1.41 (4H, m),1.58-1.63 (4H, m), 2.41 (3H, s), 2.65 (3H, s), 3.32 (4H, t, J=7.7 Hz),3.89 (3H, s), 6.16 (1H, d, J=2.2 Hz), 6.29 (1H, dd, J=2.2 Hz, 8.8 Hz),7.10 (1H, d, J=15.9 Hz), 7.44 (1H, d, J=15.9 Hz), 7.46 (1H, d, J=8.8Hz), 7.49 (1H, s), 7.56 (1H, s), 10.17 (1H, s)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 19.3, 19.4, 20.4, 29.5, 50.9, 55.3,94.7, 104.6, 113.7, 120.1, 127.5, 128.0, 131.8, 132.8, 134.0, 134.8,138.1, 143.4, 149.7, 158.7, 192.2 (10-4)2-[4-[2-[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2,5-dimethylphenyl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 6 ml of ethanol and 2 ml of tetrahydrofuran were dissolved 250 mg(0.64 mmol) of 4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2,5-dimethylbenzaldehyde and 140 mg (0.70 mmol) of2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene) propanedinitrile. To thismixture was added 49 mg of ammonium acetate, and the mixture was stirredat 70° C. for 4 hours. The solvent was evaporated off, and the residuewas purified by silica gel column chromatography and washed with ethanolto give 205 mg of a black powder (yield: 56.2%; mp: 242-244° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.7 Hz), 1.36-1.42 (4H, m),1.59-1.64 (4H, m), 1.79 (6H, s), 2.42 (3H, s), 2.47 (3H, s), 3.33 (4H,t, J=7.7 Hz), 3.90 (3H, s), 6.15 (1H, s), 6.30 (1H, d, J=8.8 Hz), 6.89(1H, d, J=15.9 Hz), 7.10 (1H, d, J=15.9 Hz), 7.47 (1H, d, J=8.8 Hz),7.49 (1H, d, J=15.9 Hz), 7.50 (1H, s), 7.53 (1H, s), 8.03 (1H, d, J=15.9Hz) ¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 19.4, 19.6, 20.4, 26.6, 29.6,50.9, 55.3, 56.6, 94.5, 97.3, 104.7, 111.0, 111.3, 112.1, 112.9, 113.5,119.6, 126.8, 128.2, 128.25, 128.28, 130.0, 133.8, 137.7, 143.4, 144.8,150.1, 159.0, 174.2, 175.8

Example 112-[4-[2-[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2,5-dimethylphenyl]vinyl]-3-cyano-5-methyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 9 ml of ethanol and 3 ml of tetrahydrofuran were dissolved 440 mg(1.12 mmol) of 4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2,5-dimethylbenzaldehyde and 310 mg (1.22 mmol) of2-(3-cyano-4,5-dimethyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.After the mixture was stirred at 70° C. for 6 hours, the solvent wasevaporated off. The residue was purified by silica gel columnchromatography and washed with ethanol to give 522 mg of a black powder(yield: 74.3%; mp: 205-207° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.7 Hz), 1.36-1.42 (4H, m),1.60-1.65 (4H, m), 1.96 (3H, s), 2.42 (3H, s), 2.48 (3H, s), 3.33 (4H,t, J=7.7 Hz), 3.90 (3H, s), 6.15 (1H, d, J=2.2 Hz), 6.30 (1H, dd, J=2.2Hz, 8.8 Hz), 6.84 (1H, d, J=15.9 Hz), 7.11 (1H, d, J=15.9 Hz), 7.48 (1H,d, J=8.8 Hz), 7.50 (1H, s), 7.55 (1H, s), 7.55 (1H, d, J=15.9 Hz), 8.43(1H, d, J=15.9 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 19.2, 19.4, 19.7, 20.3, 29.6, 50.9,55.3, 59.3, 94.4, 98.1, 104.8, 110.2, 110.8, 110.9, 111.5, 119.3, 126.8,128.4, 128.6, 129.2, 130.1, 134.0, 139.3, 144.7, 147.0, 150.3, 159.2,163.7, 175.0

Example 122-[4-[2-[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2,5-dimethylphenyl]vinyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 9 ml of ethanol and 3 ml of tetrahydrofuran were dissolved 400 mg(1.02 mmol) of 4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2,5-dimethylbenzaldehyde and 360 mg (1.14 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.The mixture was stirred at 70° C. for 2 hours. The solvent wasevaporated off and the residue was washed with ethanol. The residue waspurified by silica gel column chromatography to give 441 mg of a blackpowder (yield: 62.8%; mp: 177-179° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.35-1.41 (4H, m),1.58-1.63 (4H, m), 2.14 (3H, s), 2.38 (3H, s), 3.32 (4H, t, J=7.7 Hz),3.88 (3H, s), 6.13 (1H, d, J=2.2 Hz), 6.29 (1H, dd, J=2.2 Hz, J=8.8 Hz),7.00 (1H, d, J=15.4 Hz), 7.08 (1H, d, J=15.9 Hz), 7.45-7.59 (9H, m),7.86 (1H, d, J=15.4 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 19.1, 19.6, 20.3, 29.5, 50.9, 55.3,59.6, 94.3, 99.5, 104.8, 110.3, 110.4, 110.7, 112.7, 113.5, 119.4,126.7, 126.9, 128.4, 128.6, 129.1, 129.6, 129.9, 130.1, 131.7, 134.0,139.1, 144.7, 148.1, 150.2, 159.1, 164.2, 175.1

Example 132-[4-[2-[5-[2-[4-dibutylamino-2-(tert-butyldiphenylsiloxy)phenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

(13-1) 4-dibutylamino-2-tert-butyldiphenylsiloxybenzaldehyde

In 40 ml of N,N-dimethylformamide were dissolved 5.39 g (21.6 mmol) of4-dibutylamino-2-hydroxybenzaldehyde and 4.08 g (60.0 mmol) ofimidazole. Next, 6.13 g (22.3 mmol) of tert-butylchlorodiphenylsilanewas added dropwise thereto with stirring at room temperature. Themixture was stirred for 3.5 hours. After the reaction mixture was pouredinto water, extraction with ethyl acetate, washing with a saturatedsaline solution, drying over anhydrous sodium sulfate, and concentrationwere performed. The residue was purified by silica gel columnchromatography to give 10.3 g of a colorless oily matter (yield: 97.7%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.74 (6H, t, J=7.1 Hz), 0.97-1.03 (4H, m),1.10 (9H, s), 1.13-1.18 (4H, m), 2.84 (4H, t, J=7.1 Hz), 5.56 (1H, d,J=2.2 Hz), 6.18 (1H, dd, J=2.2 Hz, 9.3 Hz), 7.37-7.40 (4H, m), 7.41-7.45(2H, m), 7.69-7.76 (5H, m), 10.48 (1H, s)

(13-2)Dibutyl[3-(tert-butyldiphenylsiloxy)-4-[2-(thiophene-2-yl)vinyl]phenyl]amine

In a stream of argon, to 30 ml of tetrahydrofuran was added 3.17 g ofphenyllithium (19% solution in dibutylether) (7.16 mmol), and 2.57 g(6.5 mmol) of 2-thenyl triphenylphosphonium chloride was added theretounder ice cooling. Next, 3.17 g (6.5 mmol) of4-dibutylamino-2-tert-butyldiphenylsiloxybenzaldehyde was dissolved intetrahydrofuran and added dropwise. The mixture was stirred for 3 hours.After the reaction mixture was poured into water, extraction with ethylacetate, washing with a saturated saline solution, drying over anhydroussodium sulfate, and concentration were performed. The residue waspurified by silica gel column chromatography to give 2.32 g of ayellowish brown oily matter (yield: 62.9%).

(13-3)5-[2-[4-dibutylamino-2-(tert-butyldiphenylsiloxy)phenyl]vinyl]thiophene-2-carboaldehyde

In a stream of argon, in 25 ml of tetrahydrofuran was dissolved 2.32 g(4.09 mmol) ofdibutyl[3-(tert-butyldiphenylsiloxy)-4-[2-(thiophene-2-yl)vinyl]phenyl]amine,and 3.8 ml of n-butyllithium (1.6 mol solution in hexane) (6.08 mmol)was added dropwise thereto under cooling at −70 to −73° C. After themixture was stirred for 1 hour, 0.4 ml (5.77 mmol) ofN,N-dimethylformamide was added dropwise. The reaction mixture wasstirred for 1 hour and the temperature was allowed to rise. To thismixture, 10 ml of water was added dropwise. After the reaction mixturewas poured into water, extraction with ethyl acetate, washing with asaturated saline solution, drying over anhydrous sodium sulfate, andconcentration were performed. The residual liquid was dissolved in 200ml of ether and 100 mg of iodine pieces were added thereto. Afterstirred at room temperature, the mixture was washed with a 5% sodiumbisulfite solution and then with a saturated saline solution. Dryingover anhydrous sodium sulfate and concentration were performed. Theresidue was purified by silica gel column chromatography to give 1.99 gof a dark red oily matter (yield: 81.9%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.74 (6H, t, J=7.1 Hz), 0.97-1.03 (4H, m),1.06-1.21 (4H, m), 1.17 (9H,$), 2.82 (4H, t, J=7.1 Hz), 5.70 (1H, s,),6.18 (1H, d, J=8.8 Hz), 7.02 (1H, d, J=3.8 Hz), 7.06 (1H, d, J=15.9 Hz),7.37-7.43 (7H, m), 7.63 (1H, d, J=3.8 Hz), 7.75-7.78 (5H, m), 9.81 (1H,s)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.8, 19.6, 20.0, 26.6, 26.6, 29.2, 50.7,102.8, 105.5, 113.8, 115.1, 124.4, 127.1, 127.8, 129.0, 129.9, 132.7,135.4, 137.9, 139.6, 149.4, 155.1, 155.8, 182.2

(13-4)2-[4-[2-[5-[2-[4-dibutylamino-2-(tert-butyldiphenylsiloxy)phenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 12 ml of ethanol and 4 ml of tetrahydrofuran were dissolved 500 mg(0.84 mmol) of5-[2-[4-dibutylamino-2-(tert-butyldiphenylsiloxy)phenyl]vinyl]thiophene-2-carboaldehydeand 185 mg (0.93 mmol) of2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile. To thismixture was added 65 mg of ammonium acetate, and the mixture was stirredat room temperature for 47 hours. The solvent was evaporated off and theresidue was washed with ethanol. The residue was purified by silica gelcolumn chromatography and washed with ethanol to give 369 mg of a darkgreenish brown crystal (yield: 56.6%; mp: 218-219° C.).

¹H-NMR (600 MHz, CDCl₃) δ: 0.75 (6H, t, J=7.1 Hz), 0.98-1.04 (4H, m),1.14-1.21 (4H, m), 1.19 (9H, s), 1.74 (6H, s), 2.84 (4H, t, J=7.7 Hz),5.71 (1H, d, J=2.2 Hz), 6.21 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.52 (1H, d,J=15.4 Hz), 7.01 (1H, d, J=3.8 Hz), 7.09 (1H, d, J=15.9 Hz), 7.38-7.45(8H, m), 7.75-7.79 (5H, m), 7.82 (1H, d, J=15.9 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.8, 19.7, 20.0, 26.6, 26.7, 29.3, 50.7,55.5, 95.2, 96.7, 102.7, 105.9, 111.1, 111.2, 111.7, 112.5, 113.9,114.8, 126.3, 127.7, 127.9, 130.1, 130.9, 132.5, 135.4, 136.9, 138.0,139.3, 150.0, 155.7, 156.5, 172.7, 176.0

Example 142-[4-[2-[5-[2-[4-dibutylamino-2-(tert-butyldiphenylsiloxy)phenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5-methyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 12 ml of ethanol and 4 ml of tetrahydrofuran were dissolved 500 mg(0.84 mmol) of5-[2-[4-dibutylamino-2-(tert-butyldiphenylsiloxy)phenyl]vinyl]thiophene-2-carboaldehydeand 234 mg (0.92 mmol) of2-(3-cyano-4,5-dimethyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.The mixture was stirred with heating at 60° C. for 4.5 hours. Thesolvent was evaporated off and the residue was washed with ethanol. Theresidue was purified by silica gel column chromatography and washed withethanol to give 576 mg of a dark reddish brown crystal (yield: 82.6%;mp: 186-187° C.).

¹H-NMR (600 MHz, CDCl₃) δ: 0.76 (6H, t, J=7.1 Hz), 0.98-1.04 (4H, m),1.08-1.21 (4H, m), 1.19 (9H), 1.89 (3H, s), 2.86 (4H, t, J=7.1 Hz), 5.70(1H, d, J=2.2 Hz), 6.22 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.42 (1H, d, J=15.4Hz), 7.05 (1H, d, J=4.4 Hz), 7.10 (1H, d, J=15.4 Hz), 7.38-7.46 (7H, m),7.48 (1H, d, J=4.4 Hz), 7.74-7.76 (4H, m), 7.93 (1H, d, J=15.4 Hz), 8.18(1H, d, J=15.4 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.8, 19.3, 19.7, 20.0, 26.7, 29.3, 50.8,57.3, 93.3, 102.6, 106.2, 109.8, 110.8, 111.4, 114.0, 114.7, 121.2,127.2, 128.0, 130.1, 132.3, 132.4, 132.6, 135.4, 137.6, 140.3, 141.0,150.6, 156.2, 159.5, 161.5, 175.5

Example 152-[4-[2-[5-[2-[4-dibutylamino-2-tert-butyldiphenylsiloxy)phenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 12 ml of ethanol and 4 ml of tetrahydrofuran were dissolved 500 mg(0.84 mmol) of5-[2-[4-dibutylamino-2-(tert-butyldiphenylsiloxy)phenyl]vinyl]thiophene-2-carboaldehydeand 290 mg (0.92 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.The mixture was stirred with heating at 60° C. for 3 hours. The solventwas evaporated off and the residue was washed with ethanol. The residuewas purified by silica gel column chromatography and washed with ethanolto give 604 mg of a dark reddish brown crystal (yield: 80.6%; mp:188-200° C.).

¹H-NMR (600 MHz, CDCl₃) δ: 0.75 (6H, t, J=7.1 Hz), 0.98-1.04 (4H, m),1.10-1.21 (4H, m), 1.17 (9H, s), 2.85 (4H, t, J=7.7 Hz), 5.69 (1H, d,J=2.2 Hz), 6.21 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.52 (1H, d, J=15.9 Hz),6.98 (1H, d, J=4.4 Hz), 7.06 (1H, d, J=15.9 Hz), 7.33 (1H, d, J=4.4 Hz),7.37-7.45 (7H, m), 7.50-7.55 (5H, m), 7.73-7.75 (4H, m), 7.88-7.90 (1H,m), 7.90 (1H, d, J=15.9 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.8, 19.7, 20.0, 26.6, 29.3, 50.8, 57.5,95.9, 102.6, 106.2, 110.9, 111.1, 111.3, 114.0, 114.6, 121.2, 123.1,126.7, 127.2, 127.86, 127.95, 129.7, 129.9, 130.4, 131.4, 132.3, 132.6,135.4, 137.7, 140.3, 141.4, 150.6, 156.2, 159.6, 161.4, 175.6

Example 162-[3-cyano-4-[2-[5-[2-(8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-yl)vinyl]thiophene-2-yl]vinyl]-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

(16-1)8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-carboaldehyde

In 20 ml of 1-methyl-2-pyrrolidone was dissolved 2.5 g (11.5 mmol) of8-hydroxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-carboaldehyde,and 4.1 g (28.9 mmol) of methyl iodide and 4.8 g (34.7 mmol) ofanhydrous potassium carbonate were added thereto. The mixture wasstirred at 50° C. for 4 hours. After the reaction mixture was added towater, extraction with ethyl acetate, drying over anhydrous sodiumsulfate, and concentration were performed. The residue was purified bysilica gel column chromatography to give 2.63 g of a yellow crystal(yield: 99.0%).

¹H-NMR (600 MHz, CDCl₃) δ: 1.91-1.96 (4H, m), 2.71 (2H, t, J=6.6 Hz),2.75 (2H, t, J=6.6 Hz), 3.26-3.28 (4H, m), 3.81 (3H, s), 7.33 (1H, s),10.00 (1H, s)

¹³C-NMR (150 MHz, CDCl₃) δ: 20.8, 21.4, 27.3, 49.8, 50.1, 62.8, 112.3,116.8, 117.2, 127.0, 149.0, 160.7, 187.6

(16-2)8-methoxy-9-[2-(thiophene-2-yl)vinyl]-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine

In a stream of argon, to 30 ml of tetrahydrofuran was added 3.2 g ofphenyllithium (19% solution in dibutylether) (7.23 mmol), and 2.6 g(6.58 mmol) of 2-thenyl triphenylphosphonium chloride was added theretounder ice cooling. Next, 1.5 g (6.49 mmol) of8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-carboaldehydewas dissolved in tetrahydrofuran and added dropwise. The mixture wasstirred for 1.5 hours. After the reaction mixture was poured into water,extraction with ethyl acetate, washing with a saturated saline solution,drying over anhydrous sodium sulfate, and concentration were performed.The residue was purified by silica gel column chromatography to give1.29 g of an orange oily matter (yield: 63.9%).

(16-3)5-[2-(8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-yl)vinyl]thiophene-2-carboaldehyde

In a stream of argon, in 25 ml of tetrahydrofuran was dissolved 1.29 g(4.14 mmol) of8-methoxy-9-[2-(thiophene-2-yl)vinyl]-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine,and 3.9 ml of n-butyllithium (1.6 mol solution in hexane) (6.24 mmol)was added dropwise thereto under cooling at −70° C. After the mixturewas stirred for 1 hour, 0.43 g (5.88 mmol) of N,N-dimethylformamide wasadded dropwise thereto. The reaction mixture was stirred for 1 hour andthe temperature was allowed to rise. To this mixture, 10 ml of water wasadded dropwise. After the reaction mixture was added to water,extraction with ethyl acetate, washing with a saturated saline solution,drying over anhydrous sodium sulfate, and concentration were performed.The residual liquid was dissolved in 300 ml of ether and 50 mg of iodinepieces were added thereto. After stirred at room temperature, themixture was washed with a 5% sodium bisulfite solution and then with asaturated saline solution. Drying over anhydrous sodium sulfate andconcentration were performed. The residue was purified by silica gelcolumn chromatography to give 496 mg of a dark reddish brown oily matter(yield: 35.5%).

¹H-NMR (600 MHz, CDCl₃) δ: 1.93-1.98 (4H, m), 2.73 (2H, t, J=6.6 Hz),2.77 (2H, t, J=6.6 Hz), 3.18-3.12 (4H, m), 3.72 (3H, s), 7.02 (1H, d,J=15.9 Hz), 7.04 (1H, d, J=3.8 Hz), 7.06 (1H, s), 7.34 (1H, d, J=15.9Hz), 7.62 (1H, d, J=3.8 Hz), 9.80 (1H, s)

¹³C-NMR (150 MHz, CDCl₃) δ: 21.3, 21.4, 21.9, 27.5, 49.6, 49.9, 61.1,116.1, 124.6, 128.8, 137.6, 139.9, 155.3, 155.5, 182.3

(16-4)2-[3-cyano-4-[2-[5-[2-(8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-yl)vinyl]thiophene-2-yl]vinyl]-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 5 ml of ethanol and 1.5 ml of tetrahydrofuran were dissolved 158 mg(0.47 mmol) of5-[2-(8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-yl)vinyl]thiophene-2-carboaldehydeand 102 mg (0.51 mmol) of2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile. To thismixture was added 36 mg of ammonium acetate, and the mixture was stirredat room temperature for 42 hours. The crystal was filtrated and washedwith ethanol. The residue was purified by silica gel columnchromatography and washed with ethanol to give 150 mg of a blackpowdered crystal (yield: 62.0%; mp: 201-204° C.).

¹H-NMR (600 MHz, CDCl₃) δ: 1.75 (6H, s), 1.93-1.99 (4H, m), 2.74 (2H, t,J=6.6 Hz), 2.77 (2H, t, J=6.6 Hz), 3.22-3.25 (4H, m), 3.76 (3H, s), 6.53(1H, d, J=15.4 Hz), 7.01 (1H, d, J=3.8 Hz), 7.03 (1H, d, J=15.9 Hz),7.08 (1H, s), 7.35 (1H, d, J=15.9 Hz), 7.36 (1H, d, J=3.8 Hz), 7.77 (1H,d, J=15.9 Hz) ¹³C-NMR (150 MHz, CDCl₃) δ: 21.2, 21.3, 21.8, 26.6, 27.6,49.7, 50.0, 55.6, 61.3, 95.3, 96.8, 111.2, 111.6, 112.4, 113.9, 115.7,115.8, 117.9, 124.8, 126.7, 130.4, 137.1, 138.0, 139.4, 145.3, 155.9,156.0, 172.8, 175.9

Example 172-[3-cyano-4-[2-[5-[2-(8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-yl)vinyl]thiophene-2-yl]vinyl]-5-methyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 5 ml of ethanol and 1.5 ml of tetrahydrofuran were dissolved 135 mg(0.40 mmol) of5-[2-(8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-yl)vinyl]thiophene-2-carboaldehydeand 110 mg (0.43 mmol) of2-(3-cyano-4,5-dimethyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.The mixture was stirred with heating at 60° C. for 3.5 hours. Thesolvent was evaporated off and the residue was washed with ethanol. Theresidue was purified by silica gel column chromatography and washed withmethanol to give 178 mg of a dark brown crystal (yield: 78.1%; mp:159-161° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 1.91 (3H, s), 1.94-1.99 (4H, m), 2.74 (2H, t,J=6.0H), 2.77 (2H, t, J=6.6 Hz), 3.25-3.28 (4H, m), 3.76 (3H, s), 6.43(1H, d, J=15.4 Hz), 7.05 (1H, d, J=4.4 Hz), 7.06 (1H, d, J=15.9 Hz),7.10 (1H, s), 7.42 (1H, d, J=15.9 Hz), 7.45 (1H, d, J=4.4 Hz), 8.15 (1H,d, J=15.4 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 19.4, 21.1, 21.4, 21.8, 27.7, 49.8, 50.1,57.5, 61.5, 93.5, 93.7, 94.9, 110.1, 110.9, 111.4, 114.0, 115.7, 118.2,122.5, 125.4, 127.6, 132.1, 137.9, 140.3, 141.1, 146.0, 156.5, 158.9,161.8, 175.5

Example 182-[3-cyano-4-[2-[5-[2-(8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-yl)vinyl]thiophene-2-yl]vinyl]-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 5 ml of ethanol and 1.5 ml of tetrahydrofuran were dissolved 120 mg(0.35 mmol) of5-[2-(8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-yl)vinyl]thiophene-2-carboaldehydeand 123 mg (0.39 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.The mixture was stirred with heating at 60° C. for 3 hours. The solventwas evaporated off and the residue was washed with ethanol. The residuewas purified by silica gel column chromatography and washed with ethanolto give 100 mg of a dark brown crystal (yield: 44.4%; mp: 156-160° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 1.93-1.98 (4H, m), 2.72 (2H, t, J=6.0 Hz),2.77 (2H, t, J=6.6 Hz), 3.24-3.27 (4H, m), 3.75 (3H, s), 6.57 (1H, d,J=14.9 Hz), 6.99 (1H, d, J=3.8 Hz), 7.03 (1H, d, J=15.9 Hz), 7.07 (1H,s), 7.29 (1H, d, J=3.8 Hz), 7.39 (1H, d, J=15.9 Hz), 7.51-7.57 (5H, m,),7.77 (1H, d, J=14.9 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 21.1, 21.3, 21.7, 27.6, 49.7, 50.0, 57.7,61.5, 95.8, 104.3, 110.8, 111.3, 113.9, 115.7, 118.1, 125.3, 126.8,127.4, 129.76, 129.83, 131.5, 132.0, 137.8, 134.0, 141.6, 145.9, 156.4,158.8, 161.8, 175.5

Example 19

The 2-substituted oxybenzaldehyde compounds 19-1 to 19-4 shown in Table1 were synthesized in the same manner as in Examples 1-1, 4-1, 13-1, and16-1.

TABLE 1 Example ¹H-NMR (600 MHz, CDCl₃) δ ppm No. Structural Formula¹³C-NMR (150 MHz, CDCl₃) δ ppm 19-1

0.97 (6H, t, J = 7.7 Hz), 1.34-1.40 (4H, m), 1.39 (6H, d, J = 6.0 Hz),1.57-1.63 (4H, m), 3.32 (4H, t, J = 7.7 Hz), 4.56-4.60 (1H, m), 6.02(1H, s), 6.25 (1H, dd, J = 2.2 Hz, 8.8 Hz), 7.70 (1H, d, J = 8.8 Hz),10.15 (1H, s) 13.9, 20.3, 22.1, 29.4, 51.0, 70.8, 95.2, 99.9, 104.7,130.0, 154.0, 162.7, 187.5 19-2

0.27 (6H, s), 0.97 (6H, t, J = 7.7 Hz), 1.02 (9H, s), 1.33-1.40 (4H, m),1.56-1.62 (4H, m), 3.29 (4H, t, J = 7.7 Hz), 5.94 (1H, s), 6.30 (1H, dd,J = 2.2 Hz, 8.8 Hz), 7.68 (1H, d, J = 8.8 Hz), 10.13 (1H, s) −4.23,13.9, 18.4, 20.3, 25.7, 29.4, 51.1, 100.9, 105.8, 129.9, 161.0 187.519-3

1.21 (6H, t, J = 7.1 Hz), 1.40 (6H, d, J = 6.0 Hz), 3.41 (4H, q, J = 7.1Hz), 4.60-4.64 (1H, m), 6.06 (1H, d, J = 7.7 Hz), 6.29 (1H, d, J = 7.7Hz), 7.72 (1H, d, J = 8.8 Hz), 10.16 (1H, s) 12.6, 22.1, 45.0, 71.0,104.7, 130.2, 162.8, 187.6 19-4

0.97 (6H, t, J = 7.7 Hz), 1.34-1.40 (4H, m), 1.57-1.62 (4H, m), 1.85(3H, s), 3.31 (4H, t, J = 7.7 Hz), 4.52 (2H, s), 5.02 (1H, s), 5.11 (1H,s), 6.01 (1H, d, J = 2.2 Hz), 6.25 (1H, dd, J = 2.2 Hz, 8.8 Hz), 7.71(1H, d, J = 8.8 Hz), 10.20 (1H, s) 13.9, 19.3, 20.3, 29.4, 51.0, 71.8,93.9, 104.6, 112.8, 130.2, 140.8, 154.1, 163.3, 187.0

Example 20

The dibutyl[3-substituted oxy-4-[2-(thiophene-2-yl) vinyl]phenyl]aminecompounds 20-1 to 20-4 shown in Table 2 were synthesized in the samemanner as in Examples 1-2, 4-2, 13-2, and 16-2.

TABLE 2 Example No. Structural Formula 20-1

20-2

20-3

20-4

Example 21

The 5-[2-[2,4-disubstituted phenyl]vinyl]thiophene-2-carboaldehydecompounds 21-1 to 21-4 shown in Table 3 were synthesized in the samemanner as in Examples 1-3, 4-3, 13-3, and 16-3.

TABLE 3 Example Structural ¹H-NMR (600 MHz, CDCl₃) δ ppm No. Formula¹³C-NMR (150 MHz, CDCl₃) δ ppm 21-1

0.97 (6H, t, J = 7.7 Hz), 1.34-1.40 (4H, m), 1.41 (6H, d, J = 6.0 Hz),1.56-1.62 (4H, m), 3.29 (4H, t, J = 7.7 Hz), 4.50-4.55 (1H, m), 6.13(1H, d, J = 2.2 Hz, ), 6.26 (1H, dd, J = 2.2 Hz, 8.8 Hz), 7.01 (1H, d, J= 3.8 Hz), 7.06 (1H, d, J = 15.9 Hz), 7.37 (1H, d, J = 8.8 Hz), 7.44(1H, d, J = 15.9 Hz), 7.61 (1H, d, J = 3.8 Hz), 9.79 (1H, s) 14.0, 20.3,22.3, 29.6, 50.9, 71.1, 97.5, 105.0, 113.6, 115.7, 124.4, 128.5, 129.6,137.8, 139.6, 150.0, 156.0, 157.5, 182.3 21-2

0.25 (6H, s), 0.96 (6H, t, J = 7.7 Hz), 1.07 (9H, s), 1.33-1.39 (4H, m),1.56-1.60 (4H, m), 3.26 (4H, t, J = 7.7 Hz), 6.05 (1H, d, J = 2.2 Hz),6.29 (1H, dd, J - 2.2 Hz, 8.8 Hz), 6.96 (1H, d, J = 15.9 Hz), 6.99 (1H,d, J = 3.8 Hz), 7.40 (1H, d, J = 8.8 Hz), 7.47 (1H, d, J = 15.9 Hz),7.61 (1H, d, J = 3.8 Hz), 9.79 (1H, s) −4.1, 14.0, 18.4, 20.4, 25.9,29.6, 51.0, 102.4, 106.0, 114.6, 115.1, 124.4, 127.3, 129.1, 137.9,139.6, 149.8, 155.3, 155.7, 182.3 21-3

1.19 (6H, t, J = 7.1 Hz), 1.40 (6H, d, J = 6.0 Hz), 3.38 (4H, q, J = 7.1Hz), 4.52-4.58 (1H, m), 6.16 (1H, d, J = 2.2 Hz), 6.30 (1H, dd, J = 2.2Hz, 8.8 Hz), 7.01 (1H, d, J = 3.8 Hz), 7.06 (1H, d, J = 15.9 Hz), 7.39(1H, d, J = 8.8 Hz), 7.45 (1H, d, J = 15.9 Hz), 7.61 (1H, d, J = 3.8Hz), 9.79 (1H, s) 12.8, 22.3, 44.6, 71.2, 97.6, 105.0, 113.9, 115.7,124.4, 128.5, 129.5, 137.7, 139.6, 149.5, 155.9, 157.6, 182.3 21-4

0.97 (6H, t, J = 7.7 Hz), 1.33-1.39 (4H, m), 1.56-1.61 (4H, m), 1.88(3H, s), 3.28 (4H, t, J = 7.7 Hz), 4.50 (2H, s), 5.04 (1H, s), 5.13 (1H,s), 6.12 (1H, d, J = 2.2 Hz), 6.26 (1H, dd, J = 2.2 Hz, 8.8 Hz), 7.01(1H, d, J = 4.4 Hz), 7.07 (1H, d, J = 16.5 Hz), 7.37 (1H, d, J = 8.8Hz), 7.47 (1H, d, J = 15.9 Hz), 7.61 (1H, d, J = 4.4 Hz), 9.79 (1H, s)14.0, 19.5, 20.4, 29.6, 50.9, 72.2, 95.9, 104.8, 112.6, 112.7, 115.9,124.4, 128.4, 129.1, 137.7, 139.6, 141.2, 150.0, 155.8, 158.3, 182.3

Example 225-[2-(4-dibutylamino-2-hydroxyphenyl)vinyl]thiophene-2-carboaldehyde

In 10 ml of tetrahydrofuran was dissolved 488 mg (0.82 mmol) of5-[2-[4-dibutylamino-2-(tert-butyldiphenylsiloxy)phenyl]vinyl]thiophene-2-carboaldehyde,and 2.5 ml of tetrabutylammonium fluoride (1 mol solution intetrahydrofuran) was added dropwise thereto with stirring at roomtemperature. The mixture was stirred for 35 minutes. After the reactionmixture was poured into water, extraction with ethyl acetate, washingwith a saturated saline solution, drying over anhydrous sodium sulfate,and concentration were performed. The residue was purified by silica gelcolumn chromatography to give 274 mg of a blackish brown crystal (yield:93.6%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.96 (6H, t, J=7.7 Hz), 1.33-1.39 (4H, m),1.53-1.58 (4H, m), 3.26 (4H, t, J=7.7 Hz), 5.07 (1H, s), 6.01 (1H, s),6.26 (1H, d, J=8.8 Hz), 7.04 (1H, d, J=3.8 Hz), 7.08 (1H, d, J=15.9 Hz),7.32 (1H, d, J=8.8 Hz), 7.35 (1H, d, J=16.5 Hz), 7.62 (1H, d, J=3.8 Hz),9.80 (1H, s)

Example 235-[2-(4-dibutylamino-2-hydroxyphenyl)vinyl]thiophene-2-carboaldehyde

In 75 ml of tetrahydrofuran was dissolved 4.02 g (8.52 mmol) of5-[2-[4-dibutylamino-2-(tert-butyldimethylsiloxy)phenyl]vinyl]thiophene-2-carboaldehyde,and 25.5 ml of tetrabutylammonium fluoride (1 mol solution intetrahydrofuran) was added dropwise thereto with stirring at roomtemperature. The mixture was stirred for 1.5 hours. After the reactionmixture was poured into water, extraction with ethyl acetate, washingwith a saturated saline solution, drying over anhydrous sodium sulfate,and concentration were performed. The residue was purified by silica gelcolumn chromatography to give 2.74 g of a blackish brown crystal (yield:89.9%).

Example 245-[2-[4-dibutylamino-2-(oxiranylmethoxy)phenyl]vinyl]thiophene-2-carboaldehyde

In 10 ml of acetonitrile were dissolved 390 mg (1.09 mmol) of5-[2-(4-dibutylamino-2-hydroxyphenyl) vinyl]thiophene-2-carboaldehydeand 0.22 g (1.61 mmol) of epibromohydrin. To this mixture were added 0.3g (2.17 mmol) of anhydrous potassium carbonate and 40 mg oftetrabutylammonium iodide, and the mixture was stirred with heating at60° C. for 4 hours. After the reaction mixture was poured into water,extraction with ethyl acetate, washing with a saturated saline solution,drying over anhydrous sodium sulfate, and concentration were performed.The residue was purified by silica gel column chromatography. The oilymatter was dissolved in 50 ml of ether and 10 mg of iodine was addedthereto. The mixture was stirred for 1 hour. The mixture was washed witha 5% sodium bisulfite solution and then with a saturated salinesolution. Drying over anhydrous magnesium sulfate and concentration wereperformed. The residual liquid was purified by silica gel columnchromatography to give 264 mg of a dark reddish brown oily matter(yield: 58.5%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.34-1.39 (4H, m),1.56-1.61 (4H, m), 2.81 (1H, dd, J=2.5 Hz, 4.6 Hz), 2.96 (1H, t, J=4.6Hz), 3.30 (4H, t, J=7.7 Hz), 3.40-3.43 (1H, m), 4.05 (1H, dd, J=5.5 Hz,11.0 Hz), 4.26 (2H, dd, J=3.3 Hz, 11.5 Hz), 6.16 (1H, d, J=2.2 Hz), 6.28(1H, dd, J=2.2 Hz, 8.8 Hz), 7.04 (1H, d, J=3.8 Hz), 7.07 (1H, d, J=15.9Hz), 7.37 (1H, d, J=8.8 Hz), 7.43 (1H, d, J=15.9 Hz), 7.62 (1H, d, J=3.8Hz), 9.80 (1H, s)

Example 255-[2-[2-(3-bromo-2-hydroxypropoxy)-4-dibutylaminophenyl]vinyl]thiophene-2-carboaldehyde

In 15 ml of 1-methyl-2-pyrrolidone were dissolved 0.76 g (2.13 mmol) of5-[2-(4-dibutylamino-2-hydroxyphenyl)vinyl]thiophene-2-carboaldehyde and0.8 g (5.84 mmol) of epibromohydrin. To this mixture was added 0.59 g(4.27 mmol) of anhydrous potassium carbonate and the mixture was stirredwith heating at 60° C. for 4 hours. After the reaction mixture waspoured into water, extraction with ethyl acetate, washing with asaturated saline solution, drying over anhydrous sodium sulfate, andconcentration were performed. The residual liquid was purified by silicagel column chromatography. From the earlier fraction, 0.31 g of5-[2-[4-dibutylamino-2-(oxiranylmethoxy)phenyl]vinyl]thiophene-2-carboaldehydewas obtained. From the later fraction, 0.45 g of5-[2-[2-(3-bromo-2-hydroxypropoxy)-4-dibutylaminophenyl]vinyl]thiophene-2-carboaldehydewas obtained.

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.34-1.40 (4H, m),1.56-1.60 (4H, m), 3.30 (4H, t, J=7.7 Hz), 4.19 (1H, dd, J=3.3 Hz, 10.5Hz), 4.30 (1H, dd, J=3.8 Hz, 10.4 Hz,), 4.61-4.63 (1H, m), 4.69 (1H, t,J=8.5 Hz), 5.09-5.12 (1H, m), 6.08 (1H, d, J=2.2 Hz), 6.32 (1H, dd,J=2.2 Hz, 8.8 Hz), 7.00 (1H, d, J=15.9 Hz), 7.13 (1H, d, J=3.8 Hz), 7.31(1H, d, J=15.9 Hz), 7.37 (1H, d, J=8.8 Hz), 7.63 (1H, d, J=3.8 Hz), 9.80(1H, s)

Example 26

The 5-[2-[2,4-d]substituted phenyl]vinyl]thiophene-2-carboaldehydecompounds 26-1 to 26-3 shown in Table 4 were synthesized in the samemanner as in Examples 24 and 25.

TABLE 4 Example Structural ¹H-NMR (600 MHz, CDCl₃) δ ppm No. Formula¹³C-NMR (150 MHz, CDCl₃) δ ppm 26-1

0.95 (6H, t, J = 7.7 Hz), 1.30-1.36 (4H, m), 1.50-1.55 (4H, m), 3.25(4H, t, J = 7.7 Hz), 3.83 (3H, s), 5.08 (2H, s), 6.15 (1H, d, J = 2.2Hz), 6.25 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.94 (2H, d, J = 8.8 Hz), 6.97(1H, d, J = 3.8 Hz), 7.09 (1H, d, J = 15.9 Hz), 7.35 (1H, d, J = 8.8Hz), 7.37 (2H, d, J = 8.8 Hz), 7.43 (1H, d, J = 15.9 Hz), 7.59 (1H, d, J= 3.8 Hz), 9.78 (1H, s) 14.1, 20.4, 29.6, 51.0, 55.4, 70.4, 96.6, 105.0,112.9, 114.2, 116.3, 124.5, 128.8, 129.0, 129.3, 129.4, 137.8, 139.7,150.0, 155.9, 158.5, 159.5, 182.3 26-2

0.96 (6H, t, J = 7.1 Hz), 1.33-1.39 (4H, m), 1.56-1.60 (4H, m), 2.13(3H, s), 3.28 (4H, t, J = 7.7 Hz), 5.85 (1H, m), 6.31 (1H, d, J = 2.2Hz), 6.44 (1H, s), 6.53 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.97 (1H, d, J =15.9 Hz), 7.00 (1H, d, J = 3.8 Hz), 7.087 (1H, d, J = 15.9 Hz), 7.49(1H, d, J = 8.8 Hz), 7.61 (1H, d, J = 3.8 Hz), 9.80 (1H, s) 14.0, 18.6,20.3, 29.4, 50.8, 105.1, 109.9, 115.0, 117.1, 125.3, 126.9, 127.4,127.6, 135.8, 137.6, 140.3, 149.6, 150.5, 154.4, 156.7, 182.4 26-3

0.97 (6H, t, J = 7.7 Hz), 1.34-1.40 (4H, m), 1.57-1.62 (4H, m),1.81-1.85 (2H, m), 1.97-2.10 (2H, m), 3.30 (4H, t, J = 7.7 Hz), 3.78(2H, t, J = 6.6 Hz), 4.05 (2H, t, J = 6.0 Hz), 6.11 (1H, d, J = 2.2 Hz),6.26 (1H, dd, J = 2.2 Hz, 8.8 Hz), 7.01 (1H, d, J = 3.8 Hz), 7.08 (1H,d, J = 15.9 Hz), 7.36 (1H, d, J = 8.8 Hz), 7.43 (1H, d, J = 15.9 Hz),7.61 (1H, d, J = 3.8 Hz), 9.79 (1H, s) 14.0, 20.3, 25.9, 29.55, 29.61,50.9, 62.6, 68.0, 95.5, 104.8, 112.5, 115.9, 124.4, 128.6, 129.2, 137.8,139.6, 150.1, 155.8, 158.5, 182.3

Example 27

The secondary nonlinear optical compounds 27-1 to 27-29 shown in Table 5were synthesized in the same manner as in Examples 1-4, 2, and 3.

TABLE 5 Ex- ample Structural Formula ¹H-NMR (600 MHz, CDCl₃) δ ppm No.Melting Point ¹³C-NMR (150 MHz, CDCl₃) δ ppm 27-1

0.98 (6H, t, J = 7.7 Hz), 1.35-1.41 (4H, m), 1.44 (6H, d, J = 6.0 Hz),1.58-1.63 (4H, m), 1.75 (6H, s), 3.31 (4H, t, J = 7.7 Hz), 4.55-4.56(1H, m), 6.11 (1H, s), 6.27 (1H, d, J = 8.8 Hz), 6.52 (1H, d, J = 15..9Hz), 7.00 (1H, d, J = 4.4 Hz), 7.12 (1H, d, J = 15.9 H), 7.36 (1H, d, J= 3.8 Hz), 7.37 (1H, d, J = 8.8 Hz), 7.42 (1H, d, J = 15.9 Hz), 7.77(1H, d, J = 15.9 Hz) 14.0, 20.3, 22.3, 26.6, 29.6, 50.9, 55.4, 70.8,96.75, 96.82, 105.1, 110.9, 111.3, 111.7, 112.5, 113.5, 115.7, 126.5,129.3, 131.3, 136.9, 138.2, 139.5, 150.5, 156.7, 158.1, 172.9, 176.027-2

0.98 (6H, t, J = 7.7 Hz), 1.35-1.41 (4H, m), 1.45 (6H, d, J = 6.0 Hz),1.59-1.64 (4H, m), 1.91 (3H, s), 3.33 (4H, t, J = 7.7 Hz), 4.57-4.61(1H, m), 6.10 (1H, s), 6.28 (1H, d, J = 8.8 Hz), 6.43 (1H, d, J = 15.9Hz), 7.05 (1H, d, J = 4.4 Hz), 7.16 (1H, d, J = 15.9 Hz), 7.37 (1H, d, J= 8.8 Hz), 7.46 (1H, d, J = 4.4 Hz), 7.50 (1H, d, J = 15.9 Hz), 8.15(1H, d, J = 15.9 Hz) 14.0, 19.4, 20.3, 22.3, 29.6, 51.0, 57.2, 70.9,96.5, 105.3, 109.7, 110.9, 111.5, 113.5, 115.7, 121.1, 127.3, 129.9,133.2, 137.6, 140.4, 141.1, 151.1, 158.5, 159.8, 161.6, 164.3, 175.527-3

0.97 (6H, t, J = 7.7 Hz), 1.35-1.41 (4H, m), 1.44 (6H, d, J = 6.0 Hz),1.56-1.63 (4H, m), 3.32 (4H, t, J = 7.7 Hz), 4.56 (1H, m), 6.09 (1H, d,J = 2.2 Hz), 6.27 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.57 (1H, d, J = 14.8Hz), 6.99 (1H, d, J = 4.4 Hz), 7.12 (1H, d, J = 15.9 Hz), 7.29 (1H, d, J= 4.4 Hz), 7.35 (1H, d, J = 8.8 Hz), 7.46 (1H, d, J = 15.9 Hz),7.51-7.57 (5H, m), 7.75 (1H, d, J = 14.8 Hz) 14.0, 20.3, 22.2, 29.6,51.0, 57.4, 70.8, 95.3, 96.5, 105.3, 110.9, 111.0, 111.3, 111.4, 113.5,115.7, 126.9, 127.2, 129.7, 130.0, 131.4, 133.2, 137.7, 140.2, 151.0,158.6, 159.9, 161.7, 175.5 27-4

0.27 (6H, s), 0.97 (6H, t, J = 7.1 Hz), 1.09 (9H, s), 1.34-1.40 (4H, m),1.56-1.62 (4H, m), 1.74 (6H, s), 3.28 (4H, t, J = 7.1 Hz), 6.05 (1H, d,J = 2.2 Hz), 6.31 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.51 (1H, d, J = 15.4Hz), 6.98 (1H, d, J = 3.8 Hz), 6.99 (1H, d, J = 15.9 Hz), 7.36 (1H, d, J= 3.8 Hz), 7.40 (1H, d, J = 8.8 Hz), 7.50 (1H, d, J = 15.9 Hz), 7.76(1H, d, J = 15.4 Hz) −4.1, 14.0, 18.5, 20.3, 25.9, 26.6, 29.6, 51.0,55.5, 95.3, 96.8, 102.1, 106.2, 111.2, 111.6, 112.4, 114.7, 114.9,126.2, 127.8, 130.9, 136.9, 137.8, 139.3, 150.4, 155.9, 156.3, 172.7,175.9 27-5

0.28 (6H, s), 0.97 (6H, t, J = 7.1 Hz), 1.09 (9H, s), 1.34-1.40 (4H, m),1.57-1.62 (4H, m), 1.90 (3H, s), 3.29 (4H, t, J = 7.1 Hz), 6.04 (1H, d,J = 2.2 Hz), 6.32 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.42 (1H, d, J = 15.4Hz), 7.01 (1H, d, J = 15.9 Hz), 7.02 (1H, d, J = 3.8 Hz), 7.42 (1H, d, J= 8.8 Hz), 7.45 (1H, d, J = 3.8 Hz), 7.59 (1H, d, J = 15.9 Hz), 8.15(1H, d, J = 15.4 Hz) −4.1, 14.0, 18.5, 19.3, 20.3, 25.8, 29.6, 51.1,57.4, 93.3, 93.6, 94.8,102.0, 106.5, 109.9, 110.8, 111.3, 111.4, 114.7,123.1, 127.1, 128.2, 132.6, 137.6, 140.1, 141.0, 150.9, 156.4, 159.2,161.6, 175.4 27-6

0.27 (6H, s), 0.97 (6H, t, J = 7.7 Hz), 1.08 (9H, s), 1.34-1.40 (4H, m),1.56-1.62 (4H, m), 3.28 (4H, t, J = 7.7 Hz), 6.03 (1H, d, J = 2.2 Hz),6.31 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.53 (1H, d, J = 15.4 Hz), 6.96 (1H,d, J = 3.8 Hz), 6.97 (1H, d, J = 15.9 Hz), 7.31 (1H, d, J = 3.8 Hz),7.40 (1H, d, J = 8.8 Hz), 7.50-7.56 (6H, m), 7.84 (1H, d, J = 15.4 Hz)−4.1, 14.0, 18.4, 20.3, 25.7, 25.8, 29.6, 51.1, 57.6, 95.3, 96.1, 101.9,106.5, 110.8, 111.2, 111.3, 114.66, 114.73, 123.1, 126.7, 127.1, 128.1,129.7, 129.9, 131.4, 132.6, 137.7, 140.1, 141.4, 150.9, 156.4, 159.3,161.6, 175.6 27-7

1.21 (6H, t, J = 7.1 Hz), 1.44 (6H, d, J = 6.0 Hz), 1.74 (6H, s), 3.40(4H, q, J = 7.1 Hz), 4.58-4.64 (1H, m), 6.15 (1H, d, J = 2.2 Hz), 6.31(1H, dd, J = 2.2 Hz, 8.8 Hz), 6.52 (1H, d, J = 15.4 Hz), 7.00 (1H, d, J= 3.8 Hz), 7.12 (1H, d, J = 15.4 Hz), 7.36 (1H, d, J = 3.8 Hz), 7.38(1H, d, J = 8.8 Hz), 7.43 (1H, d, J = 15.9 Hz), 7.76 (1H, d, J = 15.4Hz) 12.8, 22.3, 26.6, 44.7, 55.4, 70.9, 95.0, 96.77, 96.84, 105.1,110.9, 111.3, 111.7, 112.5, 113.7, 115.8, 126.5, 129.3, 131.3, 136.9,138.1, 139.5, 150.1, 156.6, 158.1, 172.9, 176.0 27-8

1.22 (6H, t, J = 7.1 Hz), 1.45 (6H, d, J = 6.0 Hz), 1.91 (3H, s), 3.42(4H, q, J = 7.1 Hz), 4.59-4.66 (1H, m), 6.14 (1H, d, J = 2.2 Hz), 6.32(1H, dd, J = 2.2 Hz, 8.8 Hz), 6.43 (1H, d, J = 15.4 Hz), 7.05 (1H, d, J= 3.8 Hz), 7.16 (1H, d, J = 15.4 Hz), 7.39 (1H, d, J = 8.8 Hz), 7.45(1H, d, J = 3.8 Hz), 7.50 (1H, d, J = 15.4 Hz), 8.14 (1H, d, J = 15.4Hz) 12.8, 19.3, 22.3, 44.8, 57.2, 70.9, 93.3, 93.5, 94.5, 96.5, 105.3,109.7, 110.9, 111.4, 113.7, 115.8, 122.1, 127.3, 130.0, 133.1, 137.6,140.3, 141.1, 150.7, 158.6, 159.7, 161.7, 175.5 27-9

1.22 (6H, t, J = 7.1 Hz), 1.44 (6H, d, J = 6.0 Hz), 3.41 (4H, q, J = 7.1Hz), 4.58-4.64 (1H, m), 6.13 (1H, d, J = 2.2 Hz), 6.30 (1H, dd, J = 2.2Hz, 8.8 Hz), 6.57 (1H, d, J = 15.4 Hz), 6.99 (1H, d, J = 3.8 Hz), 7.13(1H, d, J = 15.4 Hz), 7.29 (1H, d, J = 3.8 Hz), 7.36 (1H, d, J = 8.8Hz), 7.47 (1H, d, J = 15.4 Hz), 7.51-7.57 (5H, m), 7.76 (1H, d, J = 15.4Hz) 12.8, 22.3, 44.8, 57.4, 70.9, 95.3, 96.5, 105.3, 110.9, 111.0,111.3, 111.4, 113.7, 115.8, 122.2, 126.9, 127.2, 129.7, 129.9, 130.0,131.5, 133.2, 137.7, 140.2, 141.7, 150.6, 158.7, 159.8, 161.7, 175.527-10

0.97 (6H, t, J = 7.7 Hz), 1.34-1.40 (4H, m), 1.56-1.62 (4H, m), 1.74(6H, s), 1.88 (3H, s), 3.30 (4H, t, J = 7.7 Hz), 4.56 (2H, s), 5.06 (1H,s), 5.13 (1H, s), 6.12 (1H, d, J = 2.2 Hz), 6.27 (1H, dd, J = 2.2 Hz,8.8 Hz), 6.52 (1H, d, J = 15.9 Hz), 7.00 (1H, d, J = 4.4 Hz), 7.11 (1H,d, J = 15.9 Hz), 7.36 (1H, d, J = 4.4 Hz), 7.37 (1H, d, J = 8.8 Hz),7.47 (1H, d, J = 15.9 Hz), 7.77 (1H, d, J = 15.9 Hz) 14.0, 19.4, 20.3,26.6, 29.6, 51.0, 55.4, 72.1, 95.1, 95.7, 96.8, 105.1, 111.0, 111.2,111.7, 112.5, 112.66, 112.74, 115.8, 126.5, 129.1, 130.9, 136.9, 138.1,139.4, 141.1, 150.5, 156.5, 158.8, 172.8, 176.0 27-11

0.98 (6H, t, J = 7.7 Hz), 1.34-1.40 (4H, m), 1.57-1.62 (4H, m), 1.88(3H, s), 1.91 (3H, s), 3.31 (4H, t, J = 7.7 Hz), 4.56 (2H, s), 5.06 (1H,s), 5.13 (1H, s), 6.11 (1H, d, J = 2.2 Hz), 6.29 (1H, dd, J = 2.2 Hz,8.8 Hz), 6.43 (1H, d, J = 14.8 Hz), 7.05 (1H, d, J = 4.4 Hz), 7.15 (1H,d, J = 15.9 Hz), 7.38 (1H, d, J = 8.8 Hz), 7.45 (1H, d, J = 4.4 Hz),7.55 (1H, d, J = 15.9 Hz), 8.14 (1H, d, J = 14.8 Hz) 14.0, 19.3, 19.4,20.3, 29.6, 51.1, 57.2, 72.2, 93.3, 93.5, 94.6, 95.6, 105.4, 109.8,110.9, 111.4, 112.7, 112.8, 115.8, 121.2, 127.3, 129.7, 132.6, 137.7,140.3, 141.0, 141.1, 151.0, 159.2, 159.5, 161.7, 175.5 27-12

0.97 (6H, t, J = 7.7 Hz), 1.33-1.40 (4H, m), 1.56-1.61 (4H, m), 1.87(3H, s), 3.30 (4H, t, J = 7.7 Hz), 4.55 (2H, s), 5.06 (1H, s), 5.12 (1H,s), 6.10 (1H, d, J = 2.2 Hz), 6.27 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.56(1H, d, J = 15.4 Hz), 6.99 (1H, d, J = 4.4 Hz), 7.11 (1H, d, J = 15.9Hz), 7.29 (1H, d, J = 4.4 Hz), 7.36 (1H, d, J = 8.8 Hz), 7.51-7.56 (6H,m), 7.77 (1H, d, J = 15.4 Hz) 14.0, 19.4, 20.3, 29.6, 51.0, 57.4, 72.195.3, 95.6, 105.3, 110.9, 111.1, 111.2, 111.4, 112.7, 112.8, 115.8,121.2, 126.9, 127.2, 129.68, 129.73, 129.9, 131.4, 132.7, 137.7, 140.2,140.9, 141.6, 151.0, 159.2, 159.6, 161.7, 175.5 27-13

0.97 (6H, t, J = 7.7 Hz), 1.34-1.40 (4H, m), 1.56-1.60 (4H, m), 1.73(6H, s), 3.28 (4H, t, J = 7.7 Hz),5 .29 (1H, s), 6.01 (1H, s), 6.28 (1H,d, J = 8.8 Hz), 6.50 (1H, d, J = 15.9 Hz), 7.00 (1H, d, J = 3.8 Hz),7.10 (1H, d, J = 15.9 Hz), 7.33 (1H, d, J = 8.8 Hz), 7.35 (1H, d, J =3.8 Hz), 7.38 (1H, d, J = 15.9 Hz), 7.77 (1H, d, J = 15.9 Hz) 14.0,20.3, 26.6, 29.5, 50.9, 55.3, 95.1, 96.9, 98.2, 105.8, 111.0, 111.1,111.3, 111.7, 112.5, 116.0, 126.6, 129.3, 130.5, 137.1, 138.1, 139.5,150.5, 155.8, 156.3, 172.9, 176.0 27-14

0.97 (6H, t, J = 7.7 Hz), 1.34-1.40 (4H, m), 1.57-1.62 (4H, m), 1.90(3H, s), 3.30 (4H, t, J = 7.7 Hz), 5.36 (1H, s), 6.00 (1H, s), 6.29 (1H,d, J = 8.8 Hz), 6.43 (1H, d, J = 15.4 Hz), 7.06 (1H, d, J = 3.8 Hz),7.14 (1H, d, J = 15.9 Hz), 7.35 (1H, d, J = 8.8 Hz), 7.45 (1H, d, J =3.8 Hz), 7.46 (1H, d, J = 15.9 Hz), 8.15 (1H, d, J = 15.4 Hz) 14.0,19.3, 20.7, 29.5, 50.9, 57.0, 94.8, 98.1, 106.1, 109.9, 110.8, 111.0,111.4, 116.0, 127.4, 129.8, 132.2, 137.8, 140.3, 141.2, 150.9, 156.3,159.3, 161.7, 175.5 27-15

0.96 (6H, t, J = 7.7 Hz), 1.33-1.40 (4H, m), 1.56-1.61 (4H, m), 3.29(4H, t, J = 7.7 Hz), 5.30 (1H, s), 5.99 (1H, s), 6.28 (1H, d, J = 8.8Hz), 6.54 (1H, d, J = 15.4 Hz), 7.00 (1H, d, J = 4.4 Hz), 7.11 (1H, d, J= 15.9 Hz), 7.30 (1H, d, J = 3.8 Hz), 7.32 (1H, d, J = 8.8 Hz), 7.43(1H, d, J = 15.9 Hz), 7.50-7.53 (5H, m), 7.80 (1H, d, J = 15.4 Hz) 14.0,20.3, 29.6, 50.9, 57.4, 95.3, 98.1, 106.1, 110.9, 111.1, 111.27, 111.33,116.0, 126.8, 127.4, 129.7, 129.8, 131.5, 132.3, 137.8, 140.2, 141.6,150.9, 156.3, 159.4, 161.7, 175.6 27-16

0.95 (6H, t, J = 7.7 Hz), 1.30-1.36 (4H, m), 1.50-1.56 (4H, m), 1.74(6H, s), 3.26 (4H, t, J = 7.7 Hz), 3.83 (3H, s, ), 5.13 (2H, s), 6.13(1H, d, J = 2.2 H), 6.27 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.50 (1H, d, J =15.4 Hz), 6.94 (1H, d, J = 3.8 Hz), 6.94 (2H, d, J = 8.8 Hz), 7.13 (1H,d, J = 15.9 Hz), 7.33 (1H,d, J = 3.8 Hz), 7.36 (1H, d, J = 8.8 Hz), 7.38(2H, d, J = 8.8 Hz), 7.44 (1H, d, J = 15.9 Hz), 7.76 (1H, d, J = 15.9Hz) 14.0, 20.3, 26.6, 29.6, 51.0, 55.4, 70.2, 95.0, 96.3, 96.8, 105.2,111.0, 111.3, 111.7, 112.5, 112.8, 114.1, 116.1, 126.5, 128.7, 129.1,129.5, 131.1, 137.0, 138.1, 139.4, 150.5, 156.6, 158.9, 159.5, 172.8,176.0 27-17

0.95 (6H, t, J = 7.7 Hz), 1.30-1.37 (4H, m), 1.51-1.56 (4H, m), 1.89(3H, s), 3.28 (4H, t, J = 7.7 Hz), 3.83 (3H, s), 5.13 (2H, s), 6.12 (1H,d, J = 2.2 Hz), 6.28 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.41 (1H, d, J = 14.8Hz), 6.94 (2H, d, J = 8.8 Hz), 6.98 (1H, d, J = 3.8 Hz), 7.16 (1H, d, J= 15.9 Hz), 7.37 (1H, d, J = 8.8 Hz), 7.38 (2H, d, J = 8.8 Hz), 7.43(1H, d, J = 3.8 Hz), 7.52 (1H, d, J = 15.9 Hz), 8.14 (1H, d, J = 15.4Hz) 13.9, 20.3, 29.6, 51.0, 55.3, 57.4, 70.2, 96.1, 105.4, 110.9, 111.1,111.3, 111.4, 112.9, 114.1, 116.1, 121.2, 126.8, 127.3, 128.6, 128.8,129.7, 129.9, 130.1, 131.4, 132.9, 137.7, 140.1, 141.6, 151.0, 159.5,159.7, 161.6, 168.3, 175.5 27-18

0.95 (6H, t, J = 7.7 Hz), 1.30-1.36 (4H, m), 1.50-1.55 (4H, m), 3.27(4H, t, J = 7.7 Hz), 3.82 (3H, s), 5.11 (2H, s), 6.11 (1H, d, J = 2.2Hz), 6.26 (1H, dd, J = 2.2 Hz, 8.8 Hz, ), 6.54 (1H, d, J = 14.8 Hz),6.92 (1H, d, J = 3.8 Hz), 6.93 (2H, d, J = 8.8 Hz), 7.13 (1H, d, J =15.4 Hz), 7.28 (1H, d, J = 3.8 Hz), 7.34 (1H, d, J = 8.8 Hz), 7.38 (2H,d, J = 8.8 Hz), 7.47- 7.56 (6H, m), 7.79 (1H, d, J = 14.3 Hz) 14.0,19.3, 20.3, 29.6, 51.0, 55.3, 57.2, 70.3, 93.3, 93.5, 94.5, 96.1, 105.4,109.8, 110.9, 111.4, 112.9, 114.1, 116.0, 123.1, 127.4, 128.7, 128.9,130.1, 132.9, 137.7, 140.3, 141.1, 151.0, 159.3, 159.5, 159.6, 161.6,175.5 27-19

0.97 (6H, t, J = 7.1 Hz), 1.35-1.41 (4H, m), 1.58-1.63 (4H, m), 1.74(6H, s), 2.81 (1H, dd, J = 2.6 Hz, 4.9 Hz), 2.98 (1H, t, J = 4.4 Hz),3.32 (4H, t, J = 7.1 Hz), 3.44-3.46 (1H, m), 4.00 (1H, dd, J = 6.0 Hz,11.5 Hz, ), 4.38 (1H, dd, J = 2.7 Hz, 11.5 Hz), 6.17 (1H, d, J = 2.2Hz), 6.30 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.52 (1H, d, J = 15.9 Hz), 7.01(1H, d, J = 3.8 Hz), 7.11 (1H, d, J = 15.9 Hz), 7.36 (1H, d, J = 3.8Hz), 7.38 (1H, d, J = 8.8 Hz), 7.44 (1H, d, J = 15.9 Hz), 7.78 (1H, d, J= 15.4 Hz) 14.0, 20.3, 26.6, 29.5, 44.7, 50.4, 50.9, 55.5, 69.5, 95.1,95.8, 96.8, 105.6, 111.1, 111.3, 111.7, 112.5, 112.7, 116.0, 126.6,129.1, 130.5, 137.1, 138.1, 139.5, 150.6, 156.2, 158.5, 172.9, 176.027-20

0.98 (12H, t, J = 7.7 Hz), 1.35-1.41 (8H, m), 1.58-1.63 (8H, m), 1.91(6H, s), 2.79-2.82 (2H, m), 2.98 (2H, t, J = 4.4 Hz), 3.33 (8H, t, J =7.7 Hz), 3.44-3.46 (2H, m), 3.97-4.02 (2H, m), 4.41 (2H, dd, J = 2.7 Hz,11.4 Hz), 6.17 (2H, s), 6.31 (2H, d, J = 8.8 Hz), 6.42 (1H, d, J = 15.9Hz), 6.43 (1H, d, J = 15.9 Hz), 7.01 (2H, d, J = 3.8 Hz), 7.14 (2H, d, J= 15.9 Hz), 7.38 (1H, d, J = 8.8 Hz), 7.39 (1H, d, J = 8.8 Hz), 7.45(2H, d, J = 3.8 Hz), 7.50 (1H, d, J = 15.9 Hz), 7.51 (1H, d, J = 15.9Hz), 8.14 (1H, d, J = 15.4 Hz) 8.15 (1H, d, J = 15.4 Hz) 14.0, 19.3,20.3, 29.6, 44.6, 50.4, 51.0, 57.4, 69.5, 93.4, 95.6, 105.8, 109.9,110.8, 111.4, 112.7, 116.0, 121.2, 123.1, 127.4, 129.59, 129.63, 132.2,137.8, 140.2, 141.1, 151.1, 158.9, 159.2, 161.7, 175.4 27-21

0.97 (6H, t, J = 7.1 Hz), 1.35-1.41 (4H, m), 1.56-1.63 (4H, m),2.79-2.80 (1H, m), 2.97-2.98 (1H, m), 3.33 (4H, t, J = 7.1 Hz), 3.43(1H, bs), 3.98-4.02 (1H, m), 4.39 (1H, dd, J = 3.3 Hz, 11.5 Hz), 6.17(1H, s, ), 6.30 (1H, d, J = 8.8 Hz), 6.58 (1H, d, J = 15.4 Hz), 7.01(1H, d, J = 3.8 Hz), 7.11 (1H, d, J = 15.9 Hz), 7.29 (1H, d, J = 3.8Hz), 7.36 (1H, d, J = 8.8 Hz), 7.48 (1H, d, J = 15.4 Hz), 7.51-7.57 (5H,m), 7.77 (1H, d, J = 14.8 Hz) 14.0, 20.3, 29.6, 44.7, 50.3, 51.0, 57.6,69.5, 95.7, 105.8, 110.9, 111.2, 111.3, 112.8, 116.0, 123.1, 126.9,127.4, 129.7, 129.8, 129.9, 131.5, 132.3, 137.8, 140.1, 141.7, 151.1,159.0, 159.3, 161.8, 175.5 27-22

0.98 (6H, t, J = 7.1 Hz), 1.35-1.41 (4H, m), 1.58-1.63 (4H, m), 1.72(6H, s), 3.33 (4H, t, J = 7.1 Hz), 4.20 (1H, dd, J = 2.7 Hz, 10.4 Hz),4.38 (1H, dd, J = 2.7 Hz, 10.4 Hz), 4.67-4.71 (2H, m), 5.13-5.16 (1H,m), 6.08 (1H, d, J = 2.2 Hz), 6.34 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.53(1H, d, J = 15.4 Hz), 7.00 (1H, d, J = 15.9 Hz), 7.05 (1H, d, J = 3.8Hz), 7.32 (1H, d, J = 3.8 Hz), 7.38 (1H, d, J = 8.8 Hz), 7.38 (1H, d, J= 15.9 Hz), 7.85 (1H, d, J = 15.9 Hz) 14.0, 20.3, 26.3, 29.5, 50.9,55.3, 65.9, 67.3, 74.3, 94.6, 95.4, 97.2, 106.3, 111.5, 111.8, 112.5,112.6, 116.2, 126.8, 128.9, 129.3, 137.6, 138.0, 139.7, 150.4, 154.7,155.7, 157.5, 173.1, 176.1 27-23

0.98 (12H, t, J = 7.7 Hz), 1.36-1.42 (8H, m), 1.59-1.64 (8H, m), 1.91(6H, s), 3.34 (8H, t, J = 7.7 Hz), 4.18-4.21 (2H, m), 4.37-4.40 (2H, m),4.69 (4H, t, J = 4.7 Hz), 5.13-5.14 (2H, m), 6.07 (1H, d, J = 2.2 Hz),6.08 (1H, d, J = 2.2 Hz), 6.35 (2H, d, J = 8.8 Hz), 6.46 (1H, d, J =15.4 Hz), 6.47 (1H, d, J = 15.4 Hz), 7.02 (1H, d, J = 15.9 Hz), 7.04(1H, d, J = 15.9 Hz), 7.11 (1H, d, J = 3.8 Hz), 7.13 (1H, d, J = 3.8Hz), 7.38 (2H, d, J = 8.8 Hz), 7.39 (1H, d, J = 3.8 Hz), 7.40 (1H, d, J= 3.8 Hz), 7.44 (1H, d, J = 15.9 Hz), 7.47 (1H, d, J = 15.9 Hz), 8.12(1H, d, J = 15.9 Hz), 8.17 (1H, d, J = 15.9 Hz) 14.0, 19.0, 19.1, 20.3,29.5, 51.0, 57.2, 65.9, 67.2, 67.5, 74.2, 95.1, 95.3, 106.37, 106.42,110.1, 110.9, 111.4, 112.46, 112.57, 115.9, 116.1, 121.2, 127.6, 129.2,129.5, 130.9, 131.0, 138.2, 138.3, 140.2, 141.2, 150.9, 154.6, 154.6,157.8, 157.9, 158.7, 158.8, 161.8, 175.5, 175.6 27-24

0.98 (12H, t, J = 7.7 Hz), 1.35-1.41 (8H, m), 1.58-1.63 (8H, m), 3.33(8H, t, J = 7.7 Hz), 4.17-4.20 (2H, m), 4.36-4.39 (2H, m), 4.67- 4.70(4H, m), 5.12-5.15 (2H, m), 6.05 (1H, d, J = 2.2 Hz), 6.06 (1H, d, J =2.2 Hz), 6.32 (1H, d, 8.8 Hz), 6.33 (1H, d, 8.8 Hz), 6.60 (1H, d, J =15.4 Hz), 6.63 (1H, d, J = 15.4 Hz), 6.99 (1H, d, J = 15.9 Hz), 7.00(1H, d, J = 15.9 Hz), 7.09 (1H, d, J = 3.8 Hz), 7.10 (1H, d, J = 3.8Hz), 7.27 (2H, d, J = 3.8 Hz), 7.30 (1H, d, J = 8.8 Hz), 7.31 (1H, d, J= 8.8 Hz), 7.39 (1H, d, J = 15.9 Hz), 7.42 (1H, d, J = 15.9 Hz),7.52-7.57 (10H, m), 7.82 (1H, d, J = 15.9 Hz), 7.85 (1H, d, J = 15.9 Hz)14.0, 20.3, 29.5, 51.0, 57.5, 66.0, 67.38, 67.43, 74.1, 95.0, 95.2,106.3, 110.9, 111.3, 111.4, 112.6, 116.2, 116.3, 121.1, 123.0, 126.65,126.73 127.6, 129.6, 129.72, 129.75, 131.2, 131.4, 138.21, 138.24,141.7, 150.8, 154.5, 158.0, 158.86, 158.93, 161.8, 175.56, 175.59 27-25

0.97 (6H, t, J = 7.7 Hz), 1.33-1.40 (4H, m), 1.56-1.61 (4H, m), 1.75(6H, s), 2.14 (3H, s), 3.30 (4H, t, J = 7.7 Hz), 5.89 (1H, m), 6.31 (1H,d, J = 2.2 Hz), 6.47 (1H, s), 6.54 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.57(1H, d, J = 15.4 Hz), 6.99 (1H, d, J = 15.9 Hz), 7.00 (1H, d, J = 3.8Hz), 7.07 (1H, d, J = 15.9 Hz), 7.35 (1H, d, J = 3.8 Hz), 7.49 (1H, d, J= 8.8 Hz), 7.72 (1H, d, J = 15.9 Hz) 14.0, 18.5, 20.3, 26.6, 29.4, 50.9,56.1, 96.3, 96.9, 105.2, 110.0, 111.0, 111.4, 111.8, 112.2, 115.1,117.0, 127.0, 127.7, 128.0, 128.2, 135.8, 137.4, 137.5, 139.3, 145.0,150.8, 154.4, 165.7, 172.9, 175.7 27-26

0.97 (6H, t, J = 7.7 Hz), 1.34-1.40 (4H, m), 1.56-1.62 (4H, m), 1.92(3H, s), 2.14 (3H, s), 3.31 (4H, t, J = 7.7 Hz), 5.89 (1H, m), 6.32 (1H,d, J = 2.7 Hz), 6.47 (1H, s), 6.49 (1H, d, J = 15.4 Hz), 6.54 (1H, dd, J= 2.2 Hz, 8.8 Hz), 7.01 (1H, d, J = 15.4 Hz), 7.04 (1H, d, J = 3.8 Hz),7.14 (1H, d, J = 15.9 Hz), 7.45 (1H, d, J = 3.8 Hz), 7.50 (1H, d, J =8.8 Hz), 8.10 (1H, d, J = 15.4 Hz) 14.0, 18.6, 19.3, 20.3, 29.4, 50.9,58.4, 93.6, 93.8, 96.5, 105.2, 110.2, 110.4, 110.7, 110.9, 111.0, 115.0116.8, 123.0, 127.6, 127.8, 128.2, 129.5, 135.8, 138.0, 139.3, 141.2,150.3, 151.1, 156.9, 162.1, 165.6, 175.1 27-27

0.96 (6H, t, J = 7.7 Hz), 1.33-1.39 (4H, m), 1.55-1.61 (4H, m), 2.13(3H, s), 3.30 (4H, t, J = 7.7 Hz), 5.88 (1H, m), 6.31 (1H, d, J = 2.2Hz), 6.46 (1H, s), 6.53 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.62 (1H, d, J =15.4 Hz), 6.97 (1H, d, J = 4.4 Hz, ), 6.97 (1H, d, J = 15.9 Hz), 7.11(1H, d, J = 15.9 Hz), 7.27 (1H, d, J = 4.4 Hz), 7.48 (1H, d, J = 8.8Hz), 7.49-7.58 (5H, m), 7.70 (1H, d, J = 15.9 Hz) 13.9, 18.5, 20.3,29.4, 50.9, 58.7, 97.3, 105.2, 110.0, 110.5, 110.7, 111.0, 111.9, 115.0,116.8, 126.9, 127.5, 127.8, 128.2, 129.6, 129.8, 131.6, 135.8, 138.1,139.2, 141.8, 150.3, 151.1, 156.9, 162.1, 165.6, 175.2 27-28

0.98 (6H, t, J = 7.7 Hz), 1.35-1.41 (4H, m), 1.57-1.63 (4H, m),1.82-1.86 (2H, m), 1.98- 2.03 (2H, m), 3.33 (4H, t, J = 7.7 Hz), 3.79(2H, t, J = 6.6 Hz), 4.08 (2H, t, J = 6.0 Hz), 6.09 (1H, d, J = 2.2 Hz),6.27 (1H, dd, J = 2.2 Hz, 8.8 Hz), 6.60 (1H, d, J = 14.9 Hz), 6.97 (1H,d, J = 4.4 Hz), 7.11 (1H, d, J = 15.9 Hz), 7.27 (1H, d, J = 4.4 Hz),7.35 (1H, d, J = 8.8 Hz), 7.49-7.57 (6H, m), 7.67 (1H, d, J = 14.9 Hz)14.0, 20.3, 25.8, 29.5, 29.6, 50.9, 57.4, 62.5, 68.1, 95.0, 95.5, 105.3,110.9, 111.2, 111.4, 112.7, 115.6, 121.2, 123.1, 126.9, 127.3, 129.7,129.9, 131.5, 132.8, 137.7, 140.3, 141.6, 151.2, 159.5, 159.8, 161.7,175.4

Example 282-[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 5 ml of ethanol were dissolved 170 mg (0.65 mmol) of4-dibutylamino-2-methoxybenzaldehyde and 141 mg (0.71 mmol) of2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene) propanedinitrile. To thismixture was added 50 mg of ammonium acetate, and the mixture was stirredat 50° C. for 4 hours. Ethanol was evaporated off and the residue waspurified by silica gel column chromatography to give 273 mg of a darkbrown crystal (yield: 95.1%; mp: 222-226° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.99 (6H, t, J=7.7 Hz), 1.37-1.43 (4H, m),1.62-1.67 (4H, m), 1.74 (6H, s), 3.41 (4H, t, J=7.7 Hz), 3.91 (3H, s),6.05 (1H, s), 6.35 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.82 (1H, d, J=15.9 Hz),7.53 (1H, d, J=8.8 Hz), 7.95 (1H, d, J=15.9 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.3, 27.1, 29.6, 51.2, 53.1, 55.5,93.3, 96.4, 106.5, 108.1, 111.8, 112.2, 112.4, 113.3, 131.4, 143.4,154.2, 162.4, 175.0, 176.6

Example 292-[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-3-cyano-5-methyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 5 ml of ethanol were dissolved 149 mg (0.57 mmol) of4-dibutylamino-2-methoxybenzaldehyde and 158 mg (0.62 mmol) of2-(3-cyano-4,5-dimethyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.After the mixture was stirred at 50° C. for 2 hours, ethanol wasevaporated off. The residue was purified by silica gel columnchromatography to give 262 mg of a dark brown crystal (yield: 92.9%; mp:211-213° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 1.00 (6H, t, J=7.7 Hz), 1.38-1.44 (4H, m),1.63-1.69 (4H, m), 1.89 (3H, s), 3.44 (4H, t, J=7.7 Hz), 3.93 (3H, s),6.03 (1H, d, J=2.2 Hz), 6.39 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.76 (1H, b),7.51 (1H, d, J=8.8 Hz), 8.43 (1H, b)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 19.7, 20.2, 29.6, 51.5, 54.6, 55.6,93.2, 93.4, 107.4, 111.6, 112.2, 112.3, 113.7, 121.4, 123.3, 145.7,146.0, 155.3, 155.4, 163.5, 163.6, 176.3

Example 302-[4-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 5 ml of ethanol were dissolved 150 mg (0.57 mmol) of4-dibutylamino-2-methoxybenzaldehyde and 197 mg (0.63 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.After the mixture was stirred at 50° C. for 2 hours, ethanol wasevaporated off. The residue was purified by silica gel columnchromatography to give 272 mg of a dark brown crystal (yield: 85.2%; mp:191-194° C.) ¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.7 Hz),1.35-1.41 (4H, m), 1.60-1.65 (4H, m), 3.40 (4H, t, J=7.7 Hz), 3.83 (3H,s), 5.96 (1H, s), 6.32 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.87 (1H, b), 7.37(1H, b), 7.46-7.52 (5H, m), 8.12 (1H, b)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.8, 20.2, 29.6, 51.5, 54.9, 55.5, 93.2,95.7, 107.2, 111.6, 112.0, 112.1, 113.8, 121.3, 123.2, 126.8, 129.4,130.8, 131.0, 146.8, 155.3, 163.5, 163.6, 176.5

Example 315,5-dimethyl-2-oxo-4-[2-(2,4,6-trimethoxyphenyl)vinyl]-2,5-dihydrofuran-3-carbonitrile

The compound was synthesized in the same procedure as in Example 30 (mp:186° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 1.67 (6H, s), 3.91 (3H, s), 3.92 (6H, s),6.12 (2H, s), 7.36 (1H, d, J=18 Hz), 8.12 (1H, d, J=18 Hz) ¹³C-NMR (150MHz, CDCl₃) δ: 26.4, 55.5, 56.0, 86.7, 90.7, 94.8, 106.0, 112.8, 114.7,137.9, 162.0, 164.7, 167.2, 179.4

Example 322-{3-cyano-4-[2-(2,4,6-trimethoxyphenyl)vinyl]-5,5-dimethyl-2(5H)-furanylidene}propanedinitrile

The compound was synthesized in the same procedure as in Example 30 (mp:250° C.).

¹H-NMR (600 MHz, CDCl₃) δ: 1.77 (6H, s), 3.93 (3H, s), 3.94 (6H, s),6.12 (2H, s), 7.34 (1H, d, J=18 Hz), 8.09 (1H, d, J=18 Hz)

Example 334-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]-5,5-dimethyl-2-oxo-2,5-dihydrofuran-3-carbonitrile

The compound was synthesized in the same procedure as in Example 30 (mp:119-120° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 1.00 (6H, t, J=7 Hz), 1.40 (4H, m), 1.64 (6H,s), 1.67 (4H, m), 3.38 (4H, t, J=8 Hz), 3.90 (6H, s), 5.78 (2H, s), 7.18(1H, d, J=16 Hz), 8.17 (1H, d, J=16 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.2, 26.7, 29.5, 50.9, 55.6, 86.4,87.6, 90.8, 102.4, 111.0, 113.8, 138.7, 152.9, 162.6, 168.3, 179.6

Example 342-{4-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene}propanedinitrile

The compound was synthesized in the same procedure as in Example 30 (mp:216° C.).

¹H-NMR (600 MHz, CDCl₃) δ: 1.00 (6H, t, J=7 Hz), 1.41 (4H, m), 1.68 (4H,m), 1.73 (6H,$), 3.42 (4H, t, J=8 Hz), 3.92 (6H, s), 5.78 (2H, s), 7.26(1H, d, J=16 Hz), 8.14 (1H, d, J=16 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.8, 20.2, 27.2, 29.6, 51.2, 55.7, 87.9,96.1, 103.9, 110.2, 112.0, 112.9, 113.8, 140.8, 154.7, 163.6, 177.0,177.1

Example 352-[4-[4-(4-dibutylamino-2-methoxyphenyl)-1,3-butadienyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile(35-1) 3-(4-dibutylamino-2-methoxyphenyl)acrylonitrile

To 0.52 g (21.7 mmol) of sodium hydride, 20 ml of tetrahydrofuran wasadded. To this mixture, 3.87 g (21.4 mmol) of diethylcyanomethylphosphonate was added dropwise under ice cooling, and themixture was stirred for 25 minutes. Next, 2.8 g (10.6 mmol) of4-dibutylamino-2-methoxybenzaldehyde in tetrahydrofuran was addeddropwise, and the mixture was stirred for 1 hour. To the mixture waterwas added and the mixture was subjected to extraction with ethylacetate. The extract was washed with a saturated saline solution, driedover anhydrous sodium sulfate, and concentrated. The residue waspurified by silica gel column chromatography to give 3.04 g of an orangeoily matter (yield: 100%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.1 Hz), 1.34-1.40 (4H, m),1.56-1.60 (4H, m), 3.31 (4H, t, J=7.1 Hz), 3.85 (3H, s), 5.74 (1H, d,J=16.5 Hz), 6.06 (1H, s), 6.21 (1H, d, J=8.8 Hz), 7.18 (1H, d, J=8.8Hz), 7.46 (1H, d, J=16.5 Hz) ¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.3,29.4, 50.9, 55.1, 89.2, 93.8, 104.3, 110.5, 120.9, 130.6, 146.4, 151.5,160.2

(35-2) 3-(4-dibutylamino-2-methoxyphenyl)propenal

In 40 ml of toluene was dissolved 3.0 g (10.5 mmol) of3-(4-dibutylamino-2-methoxyphenyl)acrylonitrile. To this mixture, 10.4ml of diisobutylaluminium hydride (1.5 mol solution in toluene) (15.6mmol) was added dropwise under cooling at −68 to −72° C. under argonatmosphere. The reaction mixture was stirred for 2 hours and thetemperature was allowed to rise. To the mixture, 50 ml of a 5% ammoniumchloride solution was added dropwise. The mixture was stirred for 30minutes and filtrated. The phases were separated and the organic layerwas washed with a saturated saline solution. The organic layer was driedover anhydrous sodium sulfate and concentrated. The residual liquid waspurified by silica gel column chromatography to give 2.51 g of an orangecrystal (yield: 82.8%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.7 Hz), 1.35-1.41 (4H, m),1.58-1.63 (4H, m), 3.33 (4H, t, J=7.1 Hz), 3.87 (3H, s), 6.08 (1H, s),6.26 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.61 (1H, dd, J=8.2 Hz, 15.4 Hz), 7.39(1H, d, J=8.8 Hz), 7.70 (1H, d, J=15.4 Hz), 9.55 (1H, d, J=8.2 Hz)

¹³C-NMR (150 MHz, CDCl₃) S: 13.9, 20.3, 29.4, 50.9, 55.1, 93.7, 104.8,110.9, 123.6, 130.8, 149.4, 152.3, 160.5

(35-3)2-[4-[4-(4-dibutylamino-2-methoxyphenyl)-1,3-butadienyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 5 ml of ethanol were dissolved 170 mg (0.59 mmol) of3-(4-dibutylamino-2-methoxyphenyl)propenal and 129 mg (0.65 mmol) of2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene) propanedinitrile. To thismixture was added 46 mg of ammonium acetate, and the mixture was stirredwith heating at 50° C. for 2 hours. The solvent was evaporated off andthe residue was purified by silica gel column chromatography to give 206mg of a dark greenish brown crystal (yield: 74.5%; mp: 181-184° C.)¹H-NMR (600 MHz, CDCl₃) δ: 0.99 (6H, t, J=7.7 Hz), 1.37-1.42 (4H, m),1.61-1.66 (4H, m), 1.69 (6H, s), 3.37 (4H, t, J=7.7 Hz), 3.91 (3H, s),6.06 (1H, b), 6.30 (1H, d, J=14.8 Hz), 6.32 (1H, b), 6.94 (1H, dd,J=14.9 Hz, 11.5 Hz), 7.40 (1H, d, J=8.8 Hz), 7.46 (1H, d, J=14.8 Hz),7.63 (1H, dd, J=13.7 Hz, 13.2 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.3, 26.7, 29.6, 51.2, 54.0, 55.3,96.4, 105.9, 111.9, 112.2, 113.0, 113.3, 122.9, 131.4, 145.3, 151.7,161.4, 173.4, 176.5

Example 362-[4-[4-(4-dibutylamino-2-methoxyphenyl)-1,3-butadienyl]-3-cyano-5-methyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 5 ml of ethanol were dissolved 145 mg (0.50 mmol) of3-(4-dibutylamino-2-methoxyphenyl)propenal and 140 mg (0.55 mmol) of2-(3-cyano-4,5-dimethyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.After the mixture was stirred with heating at 50° C. for 2 hours, thesolvent was evaporated off. The residue was purified by silica gelcolumn chromatography to give 242 mg of a dark greenish brown crystal(yield: 92.1%; mp: 169-170° C.).

¹H-NMR (600 MHz, CDCl₃) δ: 1.00 (6H, t, J=7.7 Hz), 1.37-1.44 (4H, m),1.62-1.68 (4H, m), 1.83 (3H, s), 3.41 (4H, t, J=7.7 Hz), 3.92 (3H, s),6.04 (1H, s), 6.18 (1H, d, J=14.8H), 6.34 (1H, dd, J=13.7 Hz, 13.2 Hz),6.35 (1H, dd, J=2.2 Hz, 8.8 Hz), 7.44 (1H, d, J=8.8 Hz), 7.63 (1H, d,J=14.8 Hz), 8.09 (1H, b)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 19.4, 20.3, 29.6, 51.3, 54.5, 55.3,92.7, 93.4, 106.7, 111.7, 112.0, 112.3, 112.5, 114.3, 121.4, 123.3,123.7, 132.5, 148.7, 154.0, 154.2, 161.2, 162.6, 176.2

Example 372-[4-[4-(4-dibutylamino-2-methoxyphenyl)-1,3-butadienyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 5 ml of ethanol were dissolved 130 mg (0.45 mmol) of3-(4-dibutylamino-2-methoxyphenyl)propenal and 156 mg (0.50 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.After the mixture was stirred with heating at 50° C. for 2 hours, thesolvent was evaporated off. The residue was purified by silica gelcolumn chromatography to give 229 mg of a dark greenish brown crystal(yield: 86.9%; mp: 190-192° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.99 (6H, t, J=7.7 Hz), 1.36-1.43 (4H, m),1.60-1.66 (4H, m), 3.40 (4H, t, J=7.7 Hz), 3.89 (3H, s), 6.01 (1H, s),6.26 (1H, d, J=13.7 Hz), 6.31 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.92 (1H, dd,J=14.3 Hz, 13.2 Hz), 7.38 (1H, d, J=8.8 Hz), 7.48-7.52 (6H, m), 7.90(1H, b)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.3, 29.6, 51.3, 55.0, 55.3, 93.4,106.7, 111.7, 112.2, 112.4, 113.4, 114.4, 123.9, 126.8, 129.5, 130.6,131.0, 148.7, 154.17, 154.24, 161.1, 162.6, 176.3

Example 382-[4-[6-(4-dibutylamino-2-methoxyphenyl)-1,3,5-hexatrienyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

(38-1)

5-(4-dibutylamino-2-methoxyphenyl)-2,4-pentadienenitrile

To 200 mg (8.3 mmol) of sodium hydride, 14 ml of tetrahydrofuran wasadded. To this mixture, 1.47 g (8.3 mmol) of diethylcyanomethylphosphonate was added dropwise under ice cooling, and themixture was stirred for 20 minutes. Next, 1.02 g (3.52 mmol) of3-(4-dibutylamino-2-methoxyphenyl)propenal in tetrahydrofuran was addeddropwise. After stirred for 30 minutes, the reaction mixture was pouredinto 100 ml of water and subjected to extraction with ethyl acetate. Theextract was washed with a saturated saline solution, dried overanhydrous sodium sulfate, and concentrated. The residue was purified bysilica gel column chromatography to give 1.0 g of an orange oily matter(yield: 91.2%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.35-1.40 (4H, m),1.55-1.60 (4H, m), 3.31 (4H, t, J=7.7 Hz), 3.85 (3H, s), 4.97 and 5.20(1H, d, J=15.4 Hz), 6.04 (1H, s), 6.22-6.26 (1H, m), 6.71 and 6.73 (1H,dd, J=0.7 Hz, 15.4 Hz), 7.07-7.18 (2H, m), 7.29 and 7.42 (1H, d, J=8.8Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.5, 50.8, 55.2, 92.8, 94.1,104.6, 104.7, 111.9, 119.8, 128.0, 129.2, 129.3, 137.4, 137.6, 150.7,152.6, 159.6

(38-2) 5-(4-dibutylamino-2-methoxyphenyl)-2,4-pentadienal

In 25 ml of toluene was dissolved 1.0 g (3.2 mmol) of5-(4-dibutylamino-2-methoxyphenyl)-2,4-pentadienenitrile. To thismixture, 3.2 ml of diisobutylaluminium hydride (1.5 mol solution intoluene) (4.8 mmol) was added dropwise under cooling at −73 to −76° C.under argon atmosphere. The reaction mixture was stirred for 1 hour andthe temperature was allowed to rise. To the mixture, 30 ml of a 5%ammonium chloride solution was added dropwise. The mixture was stirredfor 30 minutes and filtrated. The phases were separated. The organiclayer was washed with a saturated saline solution, dried over anhydroussodium sulfate and concentrated. The residual liquid was purified bysilica gel column chromatography to give 383 mg of a deep red crystal(yield: 37.9%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.1 Hz), 1.34-1.40 (4H, m),1.58-1.63 (4H, m), 3.32 (4H, t, J=7.1 Hz), 3.86 (3H, s), 6.09 (1H, s),6.14 (1H, dd, J=15.4 Hz, 8.2 Hz), 6.25 (1H, d, J=8.8 Hz), 6.87 (1H, dd,J=15.4 Hz, 11.5 Hz), 7.26 (1H, d, J=15.4 Hz), 7.28 (1H, d, J=15.4 Hz),7.37 (1H, d, J=8.8 Hz), 9.53 (1H, d, J=8.2 Hz)

¹³C-NMR (150 Hz, CDCl₃) δ: 13.9, 20.3, 29.5, 50.9, 55.2, 94.1, 104.7,121.4, 128.0, 129.4, 139.1, 150.9, 155.4, 159.7

(38-3)2-[4-[6-(4-dibutylamino-2-methoxyphenyl)-1,3,5-hexatrienyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 3 ml of ethanol and 1 ml of tetrahydrofuran were dissolved 146 mg(0.46 mmol) of 5-(4-dibutylamino-2-methoxyphenyl)-2,4-pentadienal and101 mg (0.51 mmol) of2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile. To thismixture was added 36 mg of ammonium acetate, and the mixture was stirredat room temperature for 19 hours. The precipitate was separated byfiltration, washed with ethanol, and purified by silica gel columnchromatography to give 140 mg of a dark greenish brown crystal (yield:60.9%; mp: 156-160° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.7 Hz), 1.35-1.41 (4H, m),1.60-1.63 (4H, m), 1.68 (6H, s), 3.35 (4H, t, J=7.7 Hz), 3.88 (3H, s),6.07 (1H, s), 6.26 (1H, d, J=8.8 Hz), 6.27 (1H, d, J=15.4 Hz), 6.45 (1H,dd, J=13.2 Hz, 12.1 Hz), 6.90 (1H, dd, J=14.8 Hz, 11.5 Hz), 7.08 (1H,dd, J=14.3 Hz, 11.5 Hz), 7.27 (1H, d, J=15.4 Hz), 7.31 (1H, d, J=8.8Hz), 7.52 (1H, dd, J=14.8 Hz, 11.5 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.3, 26.6, 29.6, 51.0, 55.3, 93.9,96.6, 105.3, 111.6, 112.0, 112.8, 113.3, 114.4, 123.3, 127.8, 130.1,140.5, 149.4, 151.9, 160.4, 173.0, 176.2

Example 392-[4-[6-(4-dibutylamino-2-methoxyphenyl)-1,3,5-hexatrienyl]-3-cyano-5-methyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

To 5 ml of ethanol were added 130 mg (0.41 mmol) of5-(4-dibutylamino-2-methoxyphenyl)-2,4-pentadienal and 115 mg (0.45mmol) of 2-(3-cyano-4,5-dimethyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile, and the mixture was stirred with heating at 50° C. for2 hours. The precipitate was separated by filtration and purified bysilica gel column chromatography to give 187 mg of a greenish browncrystal (yield: 82.5%; mp: 168-172° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.99 (6H, t, J=7.7 Hz), 1.36-1.42 (4H, m),1.61-1.66 (4H, m), 1.82 (3H, s), 3.38 (4H, t, J=7.7 Hz), 3.90 (3H, s),6.05 (1H, s), 6.15 (1H, d, J=14.3 Hz), 6.32 (1H, d, J=8.8 Hz), 6.49 (1H,dd, J=13.2 Hz, 12.6 Hz), 6.97 (1H, dd, J=14.7 Hz, 11.5 Hz), 7.23 (1H, d,J=13.2 Hz), 7.42 (1H, d, J=8.8 Hz), 7.43 (1H, d, J=13.7 Hz), 7.97 (1H,bt) ¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 19.3, 20.3, 29.6, 51.16, 51.21,55.3, 93.1, 93.6, 106.1, 111.5, 112.1, 113.0, 114.1, 121.3, 123.2,123.8, 128.6, 131.1, 144.2, 151.5, 155.4, 160.9, 161.4, 175.9

Example 402-[4-[6-(4-dibutylamino-2-methoxyphenyl)-1,3,5-hexatrienyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

To 5 ml of ethanol were added 100 mg (0.32 mmol) of5-(4-dibutylamino-2-methoxyphenyl)-2,4-pentadienal and 110 mg (0.35mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile,and the mixture was stirred with heating at 50° C. for 2.5 hours. Theprecipitate was separated by filtration and purified by silica gelcolumn chromatography to give 173 mg of a yellowish brown crystal(yield: 89.1%; mp: 208-210° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.1 Hz), 1.35-1.41 (4H, m),1.60-1.63 (4H, m), 3.37 (4H, t, J=7.7 Hz), 3.87 (3H, s), 6.03 (1H, s),6.25 (1H, d, J=14.3 Hz), 6.30 (1H, d, 8.8 Hz), 6.42 (1H, dd, J=13.2 Hz,12.1 Hz), 6.91 (1H, dd, J=14.8 Hz, 12.1 Hz), 7.10 (1H, dd, J=12.6 Hz,12.3 Hz), 7.36 (1H, d, J=13.7 Hz), 7.39 (1H, d, J=8.8 Hz), 7.48-7.53(5H, m), 7.71 (1H, b)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.3, 29.6, 51.2, 55.3, 93.6, 106.1,111.5, 112.0, 112.1, 114.4, 121.3, 123.2, 123.7, 126.6, 126.8, 128.7,129.5, 130.4, 131.1, 144.2, 151.9, 152.8, 154.2, 155.3, 160.8, 161.4,176.0

Example 412-[4-[2-[5-[4-(4-dibutylamino-2-methoxyphenyl)-1,3-butadienyl]thiophene-2-yl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile(41-1)Dibutyl[3-methoxy-4-[4-(thiophene-2-yl)-1,3-butadienyl]phenyl]amine

In a stream of argon, to 15 ml of tetrahydrofuran was added 1.68 g ofphenyllithium (19% solution in dibutylether) (3.8 mmol), and 1.37 g (3.5mmol) of 2-thenyl triphenylphosphonium chloride was added thereto underice cooling. Next, 1.0 g (3.5 mmol) of3-(4-dibutylamino-2-methoxyphenyl)propenal was dissolved intetrahydrofuran and added dropwise. The mixture was stirred under icecooling for 2 hours. After the reaction mixture was poured into water,extraction with ethyl acetate, washing with a saturated saline solution,drying over anhydrous sodium sulfate, and concentration were performed.The residue was purified by silica gel column chromatography to give0.92 g of an orange oily matter (yield: 72.0%).

(41-2)5-[4-(4-dibutylamino-2-methoxyphenyl)-1,3-butadienyl]thiophene-2-carboaldehyde

In a stream of argon, in 13 ml of tetrahydrofuran was dissolved 0.83 g(2.25 mmol) ofdibutyl[3-methoxy-4-[4-(thiophene-2-yl)-1,3-butadienyl]phenyl]amine, and2.1 ml of n-butyllithium (1.6 mol solution in hexane) (3.36 mmol) wasadded dropwise thereto under cooling at −68 to −70° C. After the mixturewas stirred for 30 minutes, 0.21 ml (2.87 mmol) of N,N-dimethylformamidewas added dropwise thereto. The reaction mixture was stirred for 1.5hours and the temperature was allowed to rise. To this mixture, 5 ml ofwater was added dropwise. After the reaction mixture was poured into 50ml of water, extraction with ethyl acetate, washing with a saturatedsaline solution, drying over anhydrous sodium sulfate, and concentrationwere performed. The residual liquid was purified by silica gel columnchromatography to give a dark reddish brown oily matter. After this oilymatter was dissolved in 100 ml of ether, 600 mg of iodine was addedthereto and the mixture was stirred. The mixture was washed with a 5%sodium bisulfite solution and then with a saturated saline solution.Drying over anhydrous sodium sulfate and concentration were performed.The residue was purified by silica gel column chromatography to give 715mg of a dark reddish brown liquid (yield: 80.1%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.34-1.40 (4H, m),1.57-1.62 (4H, m), 3.30 (4H, t, J=7.7 Hz), 3.86 (3H, s), 6.11 (1H, d,J=2.2 Hz), 6.25 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.62 (1H, d, J=15.4 Hz),6.78 (1H, dd, J=15.4 Hz, 11.0 Hz), 6.99 (1H, d, J=3.8 Hz), 7.01 (1H, dd,J=15.4 Hz, 12.7 Hz), 7.02 (1H, d, J=15.4 Hz), 7.34 (1H, d, J=8.8 Hz),7.60 (1H, d, J=3.8 Hz), 9.80 (1H, s)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.6, 50.9, 55.3, 94.5, 104.6,113.4, 120.7, 123.4, 124.9, 128.2, 132.2, 136.1, 137.6, 140.3, 149.7,154.2, 158.8, 182.3

(41-3)2-[4-[2-[5-[4-(4-dibutylamino-2-methoxyphenyl)-1,3-butadienyl]thiophene-2-yl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 7 ml of ethanol and 2 ml of tetrahydrofuran were dissolved 248 mg(0.62 mmol) of5-[4-(4-dibutylamino-2-methoxyphenyl)-1,3-butadienyl]thiophene-2-carboaldehydeand 137 mg (0.61 mmol) of 2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile. To this mixture was added 50 mg of ammonium acetate,and the mixture was stirred with heating at 50° C. for 4 hours. Theproduct was separated by filtration, washed with ethanol, and purifiedby silica gel column chromatography to give 241 mg of a dark browncrystal (yield: 66.8%; mp: 185-187° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.34-1.41 (4H, m),1.58-1.63 (4H, m), 1.74 (6H, s), 3.32 (4H, t, J=7.7 Hz), 3.37 (3H, s),6.11 (1H, d, J=2.2 Hz), 6.26 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.51 (1H, d,J=15.9 Hz), 6.62 (1H, d, J=15.4 Hz), 6.81 (1H, dd, J=14.8 Hz, 11.0 Hz),6.96 (1H, d, J=3.8 Hz), 7.02 (1H, dd, J=14.8 Hz, 11.0H), 7.07 (1H, d,J=14.8 Hz), 7.34 (1H, d, J=3.8 Hz), 7.35 (1H, d, J=8.8 Hz), 7.76 (1H, d,J=15.4 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.3, 26.5, 29.6, 50.9, 55.2, 55.7,94.3, 95.6, 96.9, 104.8, 111.2, 111.5, 112.4, 113.3, 120.4, 123.3,126.9, 128.6, 133.9, 137.6, 137.7, 137.8, 139.2, 150.2, 154.5, 159.1,172.7, 175.8

Example 422-[4-[2-[5-[4-(4-dibutylamino-2-methoxyphenyl)-1,3-butadienyl]thiophene-2-yl]vinyl]-3-cyano-5-methyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 8 ml of ethanol were dissolved 230 mg (0.58 mmol) of5-[4-(4-dibutylamino-2-methoxyphenyl)-1,3-butadienyl]thiophene-2-carboaldehydeand 160 mg (0.63 mmol) of2-(3-cyano-4,5-dimethyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile. After the mixture was stirred with heating at 50° C.for 2 hours, the product was separated by filtration and washed withethanol. The product was purified by silica gel column chromatography togive 279 mg of a black crystal (yield: 76.2%; mp: 161-162° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.7 Hz), 1.35-1.41 (4H, m),1.58-1.64 (4H, m), 1.91 (3H, s), 3.33 (4H, t, J=7.7 Hz), 3.87 (3H, s),6.10 (1H, d, J=2.2 Hz), 6.27 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.43 (1H, d,J=14.8 Hz), 6.64 (1H, d, J=14.8 Hz), 6.84 (1H, dd, J=14.8 Hz, 11.0 Hz),7.00 (1H, d, J=3.8 Hz), 7.09 (1H, dd, J=14.8 Hz, 11.0 Hz), 7.14 (1H, d,J=15.4 Hz), 7.36 (1H, d, J=8.8 Hz), 7.43 (1H, d, J=3.8 Hz), 8.13 (1H, d,J=14.8 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 19.2, 20.3, 29.6, 50.9, 55.2, 57.8,94.2, 104.9, 110.4, 110.7, 111.2, 113.3, 120.4, 121.1, 123.0, 123.3,127.7, 128.9, 135.4, 138.3, 139.5, 139.8, 140.9, 150.6, 157.1, 159.4,161.7, 175.3

Example 432-[4-[2-[5-[4-(4-dibutylamino-2-methoxyphenyl)-1,3-butadienyl]thiophene-2-yl]vinyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 8 ml of ethanol were dissolved 220 mg (0.55 mmol) of5-[4-(4-dibutylamino-2-methoxyphenyl)-1,3-butadienyl]thiophene-2-carboaldehydeand 192 mg (0.61 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.After the mixture was stirred with heating at 50° C. for 2.5 hours, theproduct was separated by filtration and washed with ethanol. The productwas purified by silica gel column chromatography to give 300 mg of ablack crystal (yield: 78.1%; mp: 125-140° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.34-1.41 (4H, m),1.58-1.63 (4H, m), 3.32 (4H, t, J=7.7 Hz), 3.87 (3H, s), 6.09 (1H, d,J=2.2 Hz), 6.25 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.55 (1H, d, J=14.8 Hz),6.61 (1H, d, J=14.8 Hz), 6.83 (1H, dd, J=14.8 Hz, 11.0 Hz), 6.95 (1H, d,J=4.4 Hz), 7.07 (1H, dd, J=14.8 Hz, 11.0 Hz), 7.13 (1H, d, J=15.4 Hz),7.28 (1H, d, J=4.4 Hz), 7.34 (1H, d, J=8.8 Hz), 7.50-7.57 (5H, m), 7.79(1H, d, J=14.8 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.6, 50.9, 55.2, 58.0, 94.2,104.9, 110.7, 111.1, 111.2, 111.6, 113.4, 120.4, 121.1, 123.3, 126.8,127.6, 128.9, 129.8, 131.5, 135.4, 138.4, 139.5, 139.7, 141.4, 150.5,157.2, 159.4, 161.7, 175.4

Example 442-[4-[4-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]-1,3-butadienyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile(44-1)3-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]acrylonitrile

To 111 mg (4.63 mmol) of sodium hydride, 8 ml of tetrahydrofuran wasadded. To this mixture, 820 mg (4.63 mmol) of diethylcyanomethylphosphonate was added dropwise under ice cooling, and themixture was stirred for 30 minutes. Next, 860 mg (2.31 mmol) of5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-carboaldehyde intetrahydrofuran was added dropwise, and the mixture was stirred for 1hour. The reaction mixture was poured into water and subjected toextraction with ethyl acetate. The extract was washed with a saturatedsaline solution, dried over anhydrous sodium sulfate, and concentrated.The residue was purified by silica gel column chromatography to give 828mg of a deep red oily matter (yield: 90.7%).

(600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.34-1.40 (4H, m), 1.57-1.62(4H, m), 3.30 (4H, t, J=7.7 Hz), 3.87 (3H, s), 5.48 (1H, d, J=16.5 Hz),6.12 (1H, d, J=2.2 Hz), 6.25 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.87 (1H, d,J=3.8 Hz), 7.01 (1H, d, J=15.9 Hz), 7.07 (1H, d, J=3.8 Hz), 7.24 (1H, d,J=15.9 Hz) 7.33 (1H, d, J=8.8 Hz), 7.38 (1H, d, J=15.9 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.5, 50.9, 55.2, 91.8, 94.5,104.6, 112.7, 116.2, 118.8, 124.8, 127.5, 128.3, 132.9, 134.9, 142.8,149.8, 149.9, 158.8

(44-2)3-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]propenal

In 25 ml of toluene was dissolved 820 mg (2.08 mmol) of3-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]acrylonitrile.To this mixture, 2.1 ml of diisobutylaluminium hydride (1.5 mol solutionin toluene) (3.15 mmol) was added dropwise under cooling at −75 to −76°C. under argon atmosphere. The reaction mixture was stirred for 75minutes and the temperature was allowed to rise. To the mixture, 30 mlof a 5% ammonium chloride solution was added dropwise. The mixture wasstirred for 30 minutes and filtrated. The phases were separated. Theorganic layer was washed with a saturated saline solution, dried overanhydrous sodium sulfate and concentrated. The residual liquid waspurified by silica gel column chromatography to give 230 mg of a darkreddish brown oily matter (yield: 27.8%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.34-1.40 (4H, m),1.57-1.63 (4H, m), 3.31 (4H, t, J=7.7 Hz), 3.88 (3H, s), 6.13 (1H, d,J=2.2 Hz), 6.25 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.41 (1H, dd, J=15.4 Hz, 7.7Hz), 6.93 (1H, d, J=3.3 Hz), 7.04 (1H, d, J=15.9 Hz), 7.21 (1H, d, J=3.3Hz), 7.28 (1H, d, J=15.9 Hz), 7.35 (1H, d, J=8.8 Hz), 7.50 (1H, d,J=15.4 Hz), 9.59 (1H, d, J=7.7 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.6, 50.9, 55.3, 94.5, 104.6,112.7, 116.4, 125.2, 125.7, 127.6, 128.4, 134.0, 135.9, 144.8, 149.8,151.3, 158.9, 192.8

(44-3) 2-[4-[4-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]-1,3-dibutaenyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 3 ml of ethanol and 1 ml of tetrahydrofuran were dissolved 130 mg(0.33 mmol) of3-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]propenaland 72 mg (0.36 mmol) of 2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile. To this mixture was added 26 mg of ammonium acetate,and the mixture was stirred at room temperature for 20 hours. Theproduct was separated by filtration, washed with ethanol, and purifiedby silica gel column chromatography to give 87 mg of a black crystal(yield: 46.0%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.7 Hz), 1.35-1.41 (4H, m),1.58-1.63 (4H, m), 1.70 (6H, s), 3.32 (4H, t, J=7.7 Hz), 3.89 (3H, s),6.12 (1H, d, J=2.2 Hz), 6.27 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.37 (1H, d,J=14.8 Hz), 6.69 (1H, dd, J=14.8 Hz, 11.5 Hz), 6.94 (1H, d, J=3.8 Hz),7.06 (1H, d, J=15.9 Hz), 7.16 (1H, d, J=3.8 Hz), 7.24 (1H, d, J=14.8Hz), 7.32 (1H, d, J=15.9 Hz), 7.36 (1H, d, J=8.8 Hz), 7.55 (1H, dd,J=14.8 Hz, 11.5 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 26.4, 29.6, 50.9, 55.3, 55.8,94.4, 95.8, 96.9, 104.8, 111.2, 111.5, 112.4, 112.7, 116.0, 116.3,125.5, 126.1, 128.6, 134.4, 138.1, 139.4, 148.1, 150.2, 152.5, 159.1,172.9, 175.9

Example 452-[4-[4-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]-1,3-butadienyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 4 ml of ethanol were dissolved 100 mg (0.25 mmol) of3-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]propenaland 87 mg (0.28 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile. After the mixture was stirred with heating at 50° C.for 4 hours, the product was separated by filtration and washed withethanol. The product was purified by silica gel column chromatography togive 97 mg of a black crystal (yield: 55.5%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.1 Hz), 1.35-1.41 (4H, m),1.58-1.63 (4H, m), 3.32 (4H, t, J=7.7 Hz), 3.88 (3H, s), 6.10 (1H, s),6.26 (1H, d, 8.8 Hz), 6.39 (1H, d, J=14.8 Hz), 6.65 (1H, dd, J=14.3 Hz,11.5 Hz), 6.96 (1H, d, J=3.8 Hz), 7.07 (1H, d, J=15.9 Hz), 7.20 (1H, d,J=3.8 Hz), 7.21 (1H, d, J=14.8 Hz), 7.35 (1H, d, J=8.8 Hz), 7.36 (1H, d,J=15.9 Hz), 7.48-7.57 (5H, m), 7.69 (1H, bt)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.6, 50.9, 55.2, 58.0, 94.2,96.0, 104.9, 110.7, 111.2, 112.7, 116.1, 121.1, 123.0, 126.0, 126.67,126.76, 128.9, 129.69, 129.75, 129.9, 131.4, 136.3, 138.4, 141.6, 150.5,150.8, 155.0, 159.4, 161.8, 175.5

Example 462-[4-[3-[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]-1-propenyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile(46-1)3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenone

In 15 ml of tetrahydrofuran, 1.5 g (10.85 mmol) of isophorone wasdissolved, and 3.4 g of sodium ethoxide (20% solution in ethanol) (10.0mmol) was added thereto. To this mixture, 2.6 g (9.87 mmol) of4-dibutylamino-2-methoxybenzaldehyde in tetrahydrofuran was addeddropwise with heating at 50° C., and the mixture was stirred for 4.5hours. To the mixture, 100 ml of ethyl acetate was added. Washing with asaturated saline solution, drying over anhydrous sodium sulfate, andconcentration were performed. The residue was purified by silica gelcolumn chromatography to give 1.7 g of a reddish orange oily matter(yield: 45.0%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.1 Hz), 1.34-1.40 (4H, m),1.57-1.62 (4H, m), 2.28 (2H, s), 2.49 (2H, s), 3.31 (4H, t, J=7.1 Hz),3.87 (3H, s), 5.99 (1H, s), 6.10 (1H, d, J=2.2 Hz), 6.26 (1H, dd, J=2.2Hz, 8.8 Hz), 6.75 (1H, d, J=15.9 Hz), 7.31 (1H, d, J=15.9 Hz), 7.42 (1H,d, J=8.8 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 28.6, 29.5, 33.3, 39.1, 50.8,51.5, 55.2, 94.2, 104.7, 112.5, 124.2, 124.3, 128.3, 130.5, 150.4,157.1, 159.2, 200.2

(46-2)[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]acetonitrile

To 0.23 g (9.6 mmol) of sodium hydride, 20 ml of tetrahydrofuran wasadded. To this mixture, 1.39 g (7.85 mmol) of diethylcyanomethylphosphonate was added dropwise under ice cooling. To themixture, 1.21 g (3.15 mmol) of3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenonein tetrahydrofuran was added dropwise. After the reaction mixture wasstirred at 50° C. overnight, water was added thereto and extraction withethyl acetate was performed. The extract was washed with a saturatedsaline solution, dried over anhydrous sodium sulfate, and concentrated.The residue was purified by silica gel column chromatography to give1.05 g of an orange oily matter (yield: 82.0%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.96 and 0.97 (6H, t, J=7.7 Hz), 1.00 and1.03 (6H, s), 1.34-1.40 (4H, m), 1.56-1.62 (4H, m), 2.21 and 2.33 (2H,s), 2.33 and 2.45 (2H, s), 3.28-3.31 (4H, m), 3.856 and 3.864 (3H, s),4.85 and 5.03 (1H, s), 6.11 (1H, d, J=2.2 Hz), 6.19 and 6.64 (1H, s),6.24 and 6.26 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.69 and 6.81 (1H, d, J=16.5Hz), 7.07 and 7.09 (1H, d, J=16.5 Hz), 7.36 and 7.37 (1H, d, J=8.8 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 14.2, 20.3, 21.1, 28.159, 28.197,29.6, 31.1, 31.3, 38.9, 42.2, 44.9, 50.9, 55.2, 60.4, 89.5, 91.1, 94.4,104.67, 104.74, 113.1, 118.2, 119.0, 122.1, 124.2, 125.2, 125.6, 127.1,127.4, 127.7, 128.0, 146.5, 146.9, 149.8, 158.4, 158.69, 158.73

(46-3)[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]acetaldehyde

In 10 ml of toluene was dissolved 0.3 g (0.74 mmol) of[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]acetonitrile.To this mixture, 0.74 ml of diisobutylaluminium hydride (1.5 molsolution in toluene) was added dropwise under dry ice/acetone cooling.The reaction mixture was stirred for 2 hours and the temperature wasallowed to rise. To the mixture, an ammonium chloride solution was addeddropwise. The organic layer was separated, dried over anhydrous sodiumsulfate, and concentrated. The residue was purified by silica gel columnchromatography to give 0.21 g of a dark reddish brown oily matter(yield: 71.0%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.03 and 1.06 (6H,s), 1.34-1.40 (4H, m), 1.57-1.62 (4H, m), 2.27 and 2.39 (2H, s), 2.38and 2.67 (2H, s), 3.30 (4H, m), 3.86 and 3.87 (3H, s), 5.67 and 5.89(1H, d, J=8.2 Hz), 6.11 (1H, d, J=2.2 Hz), 6.24 and 7.15 (1H, s),6.25-6.27 (1H, m), 6.76 and 6.80 (1H, d, J=16.5 Hz), 7.10 and 7.12 (1H,d, J=16.5 Hz), 7.38 and 7.40 (1H, d, J=8.8 Hz), 10.03 and 10.21 (1H, d,J=8.2 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 28.3, 28.4, 29.6, 31.1, 39.0,39.2, 39.5, 46.5, 50.8, 55.2, 94.4, 104.8, 113.2, 120.0, 123.7, 125.69,125.75, 125.9, 127.3, 127.4, 127.5, 127.91, 127.93, 147.7, 147.9, 150.0,157.3, 157.6, 158.8, 158.9, 189.8, 190.6

(46-4) 2-[4-[3-[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]-1-propenyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 6 ml of ethanol were dissolved 173 mg (0.42 mmol) of[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]acetaldehydeand 95 mg (0.48 mmol) of 2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile. To this mixture was added 34 mg of ammonium acetate,and the mixture was stirred with heating at 50° C. for 3.5 hours. Thesolvent was evaporated off and the residue was purified by silica gelcolumn chromatography to give 229 mg of a dark brown crystal (yield:91.8%; mp: 228-230° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.7 Hz), 1.03 and 1.05 (6H,s), 1.35-1.41 (4H, m), 1.58-1.63 (4H, m), 1.69 and 1.74 (6H, s), 2.34and 2.44 (2H, s), 2.42 (2H, s), 3.37 (4H, t, J=7.7 Hz), 3.88 (3H, s),6.07 and 6.32 (1H, d, J=12.6 Hz), 6.09 (1H, s), 6.15 and 6.21 (1H, d,J=14.8 Hz), 6.27 (1H, d, J=8.8; H), 6.36 and 6.78 (1H, s), 6.84 and 6.86(1H, d, J=15.9 Hz), 7.24 and 7.25 (1H, d, J=15.9 Hz), 7.42 and 7.46 (1H,d, J=8.8 Hz), 8.00 and 8.30 (1H, b)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 26.6, 28.3, 28.5, 29.6, 31.5,31.8, 39.5, 39.7, 40.0, 50.9, 54.3, 55.2, 94.1, 96.5, 105.0, 112.0,112.2, 112.9, 113.3, 114.5, 125.5, 127.3, 128.3, 129.0, 129.8, 143.4,144.1, 150.6, 150.8, 156.2, 159.4, 172.8, 176.4

Example 472-[4-[3-[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]-1-propenyl]-3-cyano-5-methyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 6 ml of ethanol were dissolved 200 mg (0.49 mmol) of[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]acetaldehydeand 136 mg (0.54 mmol) of2-(3-cyano-4,5-dimethyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.After the mixture was stirred with heating at 50° C. for 3.5 hours, thesolvent was evaporated off. The residue was purified by silica gelcolumn chromatography to give 224 mg of a dark brown crystal (yield:71.2%; mp: 196-201° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.1 Hz), 1.05 (6 H, s),1.35-1.41 (4H, m), 1.61-1.63 (4H, m), 1.82 (3H, s), 2.49 (4H, s), 3.35(4H, t, J=7.1 Hz), 3.89 (3H, s), 6.08 (1H, s), 6.12 (1H, b), 6.29 (1H,d, J=8.2 Hz), 6.38 (1H, d, J=12.6 Hz), 6.43 (1H, s), 6.89 (1H, d, J=15.9Hz), 7.42 (1H, d, J=15.9 Hz), 7.46 (1H, d, J=8.8 Hz), 8.39 (1H, b)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 14.2, 19.4, 20.3, 28.4, 29.6, 31.8,39.8, 40.1, 51.0, 55.3, 60.4, 93.9, 105.5, 111.5, 112.2, 113.2, 125.3,128.6, 129.1, 129.7, 132.8, 145.8, 151.5, 160.1, 171.2, 176.0

Example 482-[4-[3-[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]-1-propenyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

207 mg (0.51 mmol) of[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]acetaldehydeand 175 mg (0.56 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrilewere dissolved, and the mixture was stirred with heating at 50° C. for 3hours. The precipitate was separated by filtration and washed withethanol. The residue was purified by silica gel column chromatography togive 274 mg of a dark brown crystal (yield: 76.8%; mp: 164-166° C.).¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (3H, s), 0.98 (6H, t, J=7.7 Hz), 1.01(3H, s), 1.35-1.41 (4H, m), 1.59-1.64 (4H, m), 2.26-2.34 (2H, b), 2.44(2H, s), 3.35 (4H, t, J=7.7 Hz), 3.88 (3H, s), 6.07 (1H, d, J=2.2 Hz),6.25 (2H, b), 6.29 (1H, d, J=8.8 Hz), 6.37 (1H, b), 6.85 (1H, d, J=15.4Hz), 7.40 (1H, d, J=15.4 Hz), 7.45 (1H, d, J=8.8 Hz), 7.48-7.53 (5H, m),8.08 (1H, b)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.3, 28.1, 28.5, 29.6, 39.7, 39.8,51.0, 55.2, 55.3, 93.9, 105.5, 111.6, 112.2, 113.6, 114.47, 114.52,123.2, 125.3, 126.7, 128.5, 129.1, 129.5, 130.7, 131.0, 132.9, 151.5,160.2, 176.2

Example 492-[4-[3-[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-methoxy-5,5-dimethyl-2-cyclohexenylidene]-1-propenyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile(49-1)3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-methoxy-5,5-dimethyl-2-cyclohexenone

In 10 ml of ethanol, 0.32 g (13.9 mmol) of sodium was dissolved. Next,2.36 g (8.96 mmol) of 4-dibutylamino-2-methoxybenzaldehyde and 1.58 g(9.39 mmol) of 2-methoxy-3,5,5-trimethyl-2-cyclohexenone were dissolvedin ethanol and added to the mixture. The mixture was stirred withheating at 60° C. for 17 hours and concentrated. The residual liquid waspurified by silica gel column chromatography to give 2.27 g of a darkred oily matter (yield: 61.2%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.11 (6H, s),1.34-1.40 (4H, m), 1.58-1.63 (4H, m), 2.36 (2H, s), 2.56 (2H, s), 3.31(4H, t, J=7.7 Hz), 3.73 (3H, s), 3.87 (3H, s), 6.11 (1H, d, J=2.2 Hz),6.27 (1H, dd, J=2.2 Hz, 8.8 Hz), 7.23 (1H, d, J=16.5 Hz), 7.28 (1H, d,J=16.5 Hz), 7.53 (1H, d, J=8.8 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 28.5, 29.5, 32.7, 38.8, 50.9,52.1, 55.3, 60.5, 94.2, 104.8, 113.3, 118.1, 128.0, 129.6, 141.2, 147.2,150.2, 159.0, 194.5

(49-2)[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-methoxy-5,5-dimethyl-2-cyclohexenylidene]acetonitrile

To 0.18 g (7.5 mmol) of sodium hydride, 12 ml of tetrahydrofuran wasadded. To this mixture, 0.98 g (5.5 mmol) of diethylcyanomethylphosphonate was added dropwise under ice cooling. To themixture, 0.915 g (2.2 mmol) of3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-methoxy-5,5-dimethyl-2-cyclohexenonein tetrahydrofuran was added dropwise. After the mixture was stirred at60° C. for 24 hours, water was added to the mixture and extraction withethyl acetate was performed. The extract was washed with a saturatedsaline solution, dried over anhydrous sodium sulfate, and concentrated.The residue was purified by silica gel column chromatography to give0.51 g of an orange oily matter (yield: 52.9%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.04 (6H, s),1.34-1.40 (4H, m), 1.57-1.62 (4H, m), 2.39 (2H, s), 2.53 (2H, s), 3.30(4H, m), 3.63 (3H, s), 3.86 (3H, s), 5.44 (1H, s), 6.11 (1H, d, J=2.2Hz), 6.26 (1H, dd, J=2.2 Hz, 8.8 Hz), 7.05 (1H, d, J=15.9 Hz), 7.15 (1H,d, J=16.5 Hz), 7.46 (1H, d, J=8.8 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 28.1, 29.6, 30.8, 39.0, 42.7,50.9, 55.3, 60.8, 88.7, 94.4, 104.7, 113.6, 118.6, 119.1, 127.3, 127.7,131.7, 148.0, 149.8, 153.2, 158.7

(49-3)[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-methoxy-5,5-dimethyl-2-cyclohexenylidene]acetaldehyde

In 30 ml of toluene was dissolved 1.08 g (2.47 mmol) of[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-methoxy-5,5-dimethyl-2-cyclohexenylidene]acetonitrile.To this mixture, 3.6 ml of diisobutylaluminium hydride (1.5 mol solutionin toluene) was added dropwise under dry ice/acetone cooling. Themixture was stirred for 2 hours and the temperature was allowed to rise.To the mixture, a 5% ammonium chloride solution was added dropwise. Theorganic layer was separated, dried over anhydrous sodium sulfate, andconcentrated. The residue was purified by silica gel columnchromatography to give 612 mg of a dark reddish brown crystal (yield:56.3%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.07 (6H, s),1.34-1.40 (4H, m), 1.57-1.62 (4H, m), 2.43 (2H, s), 2.73 (2H, s), 3.31(4H, t, J=7.7 Hz), 3.64 (3H, s), 3.87 (3H, s), 6.12 (1H, d, J=2.2 Hz),6.27 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.30 (1H, d, J=8.2 Hz), 7.09 (1H, d,J=16.5 Hz), 7.24 (1H, d, J=16.5 Hz), 7.48 (1H, d, J=8.8 Hz), 10.07 (1H,d, J=8.2 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 28.3, 29.6, 30.7, 38.8, 39.2,50.9, 55.3, 60.9, 94.4, 104.8, 113.7, 119.2, 121.2, 127.4, 127.7, 133.8,149.0, 149.9, 151.6, 158.8, 191.1

(49-4) 2-[4-[3-[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-methoxy-5,5-dimethyl-2-cyclohexenylidene]-1-propenyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 6 ml of ethanol and 2 ml of tetrahydrofuran were dissolved 239 mg(0.54 mmol) of [3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-methoxy-5,5-dimethyl-2-cyclohexenylidene]acetaldehyde and 120mg (0.60 mmol) of2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile. To thismixture was added 42 mg of ammonium acetate, and the mixture was stirredwith heating at 50° C. for 2.5 hours. The solvent was evaporated off andthe residue was purified by silica gel column chromatography to give 279mg of a dark brown crystal (yield: 82.7%; mp: 244-246° C.).

¹H-NMR (600 MHz, CDCl₃) S: 0.98 (6H, t, J=7.7 Hz), 1.06 (6H, s),1.35-1.41 (4H, m), 1.59-1.63 (4H, m), 1.69 (6H, s), 2.27 (2H, s), 2.48(2H, s), 3.33 (4H, t, J=7.7 Hz), 3.69 (3H, s), 3.88 (3H, s), 6.10 (1H,d, J=2.2 Hz), 6.29 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.33 (1H, d, J=14.9 Hz),6.76 (1H, d, J=14.9 Hz), 7.21 (1H, d, J=14.9 Hz), 7.29 (1H, d, J=16.5Hz), 7.51 (1H, d, J=8.8 Hz), 8.00 (1H, t, J=13.9 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 26.5, 28.3, 29.6, 31.0, 39.1,40.1, 50.9, 54.7, 55.3, 61.3, 93.5, 94.2 96.6, 105.1, 111.9, 112.1,112.8, 113.9, 115.8, 119.1, 122.4, 128.2, 129.6, 137.1, 144.2, 148.8,150.5, 151.0, 159.3, 173.0, 176.3

Example 502-[4-[3-[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-methoxy-5,5-dimethyl-2-cyclohexenylidene]-1-propenyl]-3-cyano-5-methyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 5 ml of ethanol were dissolved 200 mg (0.46 mmol) of[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-methoxy-5,5-dimethyl-2-cyclohexenylidene]acetaldehydeand 127 mg (0.50 mmol) of2-(3-cyano-4,5-dimethyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.After the mixture was stirred with heating at 60° C. for 2 hours, thesolvent was evaporated off. The residue was purified by silica gelcolumn chromatography to give 226 mg of a brown crystal (yield: 73.6%;mp: 141-151° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.7 Hz), 1.06 (3H, s), 1.07(3H, s), 1.36-1.42 (4H, m), 1.60-1.65 (4H, m), 1.84 (3H, s), 2.53 (4H,s), 3.36 (4H, t, J=7.7 Hz), 3.71 (3H, s), 3.90 (3H, s), 6.09 (1H, d,J=2.2 Hz), 6.26 (1H, d, J=13.7 Hz), 6.31 (1H, dd, J=2.2 Hz, 8.8 Hz),6.81 (1H, d, J=12.6 Hz), 7.33 (1H, d, J=15.9 Hz), 7.38 (1H, d, J=16.5Hz), 7.55 (1H, d, J=8.8 Hz), 8.37 (1H, b)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 19.3, 20.3, 28.2, 29.6, 31.2, 39.4,40.2, 51.0, 55.3, 55.7, 61.5, 92.9, 93.9, 105.5, 111.4, 112.0, 112.6,114.1, 114.5, 119.0, 123.3, 128.9, 132.4, 141.7, 146.0, 151.3, 151.7,151.9, 160.1, 161.1, 175.9

Example 512-[4-[3-[3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-methoxy-5,5-dimethyl-2-cyclohexenylidene]-1-propenyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

185 mg (0.42 mmol) of3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-methoxy-5,5-dimethyl-2-cyclohexenylidene]acetaldehydeand 146 mg (0.46 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrilewere dissolved, and the mixture was stirred with heating at 60° C. for 2hours. The precipitate was separated by filtration and washed withethanol. The residue was purified by silica gel column chromatography togive 172 mg of a brown crystal (yield: 55.5%; mp: 153-158° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (3H, s), 0.98 (6H, t, J=7.7 Hz), 1.02(3H, s), 1.35-1.41 (4H, m), 1.59-1.64 (4H, m), 2.27 (1H, d, J=15.9 Hz),2.36 (1H, d, J=15.9 Hz), 2.49 (2H, s), 3.35 (4H, t, J=7.7 Hz), 3.66 (3H,s), 3.89 (3H, s), 6.08 (1H, d, J=2.2 Hz), 6.30 (1H, dd, J=2.2 Hz, 8.8Hz), 6.37 (1H, d, J=13.8 Hz), 6.72 (1H, d, J=12.6 Hz), 7.30 (1H, d,J=15.9 Hz), 7.36 (1H, d, J=15.9 Hz), 7.50-7.54 (6H, m), 8.02 (1H, b)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 28.0, 28.4, 29.6, 31.2, 39.3,51.0, 55.3, 55.9, 61.5, 91.9, 105.5, 111.4, 111.9, 114.2, 115.8, 119.0,121.2, 123.2, 123.3, 126.8, 128.9, 129.5, 130.6, 131.1, 132.5, 141.7,146.4, 151.4, 151.7, 151.8, 160.1, 161.2, 176.0

Example 522-[3-cyano-5-phenyl-5-trifluoromethyl-4-[2-[5-[2-(2,4,6-trimethoxyphenyl)vinyl]-2-thienyl]vinyl]-2(5H)-furanylidene]propanedinitrile(52-1) 2-[2-(2,4,6-trimethoxyphenyl)vinyl]thiophene

In a stream of argon, to 30 ml of tetrahydrofuran was added 0.95 g ofphenyllithium (19% solution in dibutylether) (2.15 mmol). To thismixture, 0.78 g (1.98 mmol) of thiophene-2-ylmethyltriphenylphosphoniumbromide was added under cooling. After the mixture was well-stirred,0.38 g (1.98 mmol) of 2,4,6-trimethoxybenzaldehyde dissolved in 3 ml oftetrahydrofuran was added dropwise. The mixture was reacted withstirring for 1.5 hours. After the reaction mixture was poured into 70 mlof ice water, extraction with 200 ml of chloroform, washing with asaturated saline solution, drying over anhydrous magnesium sulfate, andconcentration were performed. The residue was purified by silica gelchromatography to give 508 mg (yield: 92%) of2-[2-(2,4,6-trimethoxyphenyl)vinyl]thiophene as a colorless crystal.

¹H-NMR (600 MHz, CDCl₃) δ: 3.80 (3H, s), 3.85 (6H, s), 6.13 (2H, s),6.98 (1H, d, J=6 Hz), 7.29 (1H, s), 7.10 (1H, d, J=6 Hz), 7.25 (1H, d,J=18 Hz), 7.58 (1H, d, J=18 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 55.2, 55.7, 90.7, 107.6, 119.6, 122.9,123.0, 124.3, 127.3, 145.6, 159.4, 160.1

(52-2) 5-[2-(2,4,6-trimethoxyphenyl)vinyl]thiophene-2-carbaldehyde

In a stream of argon, in 10 ml of tetrahydrofuran was dissolved 500 mg(1.80 mmol) of 2-[2-(2,4,6-trimethoxyphenyl) vinyl]thiophene, and 1.27ml of n-butyllithium (1.6 M solution in hexane) (2.03 mmol) was addeddropwise thereto under cooling. The mixture was stirred for 1 hour. Tothis mixture, 0.16 ml (2.00 mmol) of N,N-dimethylformamide was addeddropwise and reacted. After reacted at gradually increasing temperature,the reaction mixture was stirred at room temperature for 12 hours. Themixture was poured into 50 ml of ice water and subjected to 3 times ofextraction with 200 ml of chloroform. The extract was washed with asaturated saline solution, dried over anhydrous magnesium sulfate, andconcentrated. The residue was purified by silica gel chromatography togive 380 mg (yield: 69%) of5-[2-(2,4,6-trimethoxyphenyl)vinyl]thiophene-2-carbaldehyde as a lightyellow crystal.

¹H-NMR (600 MHz, CDCl₃) δ: 3.74 (3H, s), 3.79 (6H, s), 6.03 (2H, s),6.98 (1H, d, J=3.8 Hz), 7.51 (2H, s), 7.54 (1H, d, J=3.8 Hz), 9.70 (1H,s)

(52-3)2-[3-cyano-5-phenyl-5-trifluoromethyl-4-[2-[5-[2-(2,4,6-trimethoxyphenyl)vinyl]-2-thienyl]vinyl]-2(5H)-furanylidene]propanedinitrile

To 20 ml of acetonitrile were added 304 mg (1.00 mmol) of5-[2-(2,4,6-trimethoxyphenyl)vinyl]thiophene-2-carbaldehyde, 315 mg(1.00 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile,and a catalytic amount of ammonium acetate. The mixture was stirredovernight. After the reaction, the mixture was concentrated and theresidue was purified by silica gel column chromatography to give 490 mg(yield: 82%) of the target compound2-[3-cyano-5-phenyl-5-trifluoromethyl-4-[2-[5-[2-(2,4,6-trimethoxyphenyl)vinyl]thiophene-2-yl]vinyl]-2(5H)-furanylidene]propanedinitrileas a yellow crystal.

¹H-NMR (600 MHz, CDCl₃) δ: 3.86 (3H, s), 3.89 (6H, s), 6.14 (2H, s),6.65 (1H, d, J=12 Hz), 7.04 (1H, d, J=4 Hz), 7.26 (1H, s), 7.29 (1H, d,J=4 Hz), 7.49-7.56 (5H, m), 7.61 (1H, s), 7.75 (1H, d, J=12 Hz)

Example 532-[3-cyano-5,5-dimethyl-4-[2-[5-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]-2-thienyl]vinyl]-2(5H)-furanylidene]propanedinitrile

(53-1) 4-dibutylamino-3,5-dimethoxybenzene

In a stream of argon, to 300 ml of dioxane were added 21.7 g (100 mmol)of 3,5-dimethoxybromobenzene and 13.0 g (100 mmol) of dibutylamine, and22.0 g (110 mmol) of potassium bistrimethylsilylamide was added theretowith stirring. After well-stirred, the mixture was heated under refluxwith stirring overnight. The reactant was poured into 2 L of ice waterand subjected to 3 times of extraction with 200 ml of chloroform.Washing with a saturated saline solution, drying over anhydrousmagnesium sulfate, and concentration were performed. The residue waspurified by silica gel chromatography to give 23.4 g (yield: 88%) of4-dibutylamino-3,5-dimethoxybenzene as a colorless transparent oilymatter.

¹H-NMR (600 MHz, CDCl₃) δ: 0.946 (6H, t, J=8 Hz), 1.40 (4H, m), 1.56(4H, m), 3.22 (4H, t, J=7 Hz), 3.75 (6H, s), 5.83 (3H, s)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.8, 20.2, 29.4, 50.7, 54.8, 87.0, 91.0,149.8, 161.6

(53-2) 4-dibutylamino-2,6-dimethoxybenzaldehyde

In a stream of argon, to 30 ml of N,N-dimethylformamide was added 16.0 g(104 mmol) of phosphorus oxychloride under cooling at 5 to 10° C. andstirring. After the mixture was well-stirred, 23.5 g (80.1 mmol) of4-butylamino-2,6-dimethoxybenzene dissolved in 10 ml ofN,N-dimethylformamide was added dropwise. The mixture was reacted withstirring for 1.5 hours. After the mixture was poured into 70 ml of icewater, extraction with 200 ml of chloroform, washing with a saturatedsaline solution, drying over anhydrous magnesium sulfate, andconcentration were performed. The residue was purified by silica gelchromatography to give 18.8 g (yield: 80%) of4-dibutylamino-2,6-dimethoxybenzaldehyde as a dark purple crystal (mp:55-56° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.99 (6H, t, J=8 Hz), 1.39 (4H, m), 1.62 (4H,m), 3.34 (4H, t, J=7 Hz), 3.85 (6H, s), 5.71 (2H, s), 9.98 (1H, s)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.2, 29.4, 50.8, 55.5, 86.8, 104.7,153.8, 164.2, 186.2

(53-3) 2-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]thiophene

In a stream of argon, to 30 ml of tetrahydrofuran was added 3.76 g of a19% phenyllithium solution (8.5 mmol), and 0.78 g (1.98 mmol) ofthiophene-2-ylmethyltriphenylphosphonium bromide was added thereto undercooling. After the mixture was well-stirred, 0.58 g (1.98 mmol) of4-dibutylamino-2,6-dimethoxybenzaldehyde dissolved in 3 ml oftetrahydrofuran was added dropwise. The mixture was stirred for 1.5hours. After the mixture was poured into 70 ml of ice water, extractionwith 200 ml of chloroform, washing with a saturated saline solution,drying over anhydrous magnesium sulfate, and concentration wereperformed. The residue was purified by silica gel chromatography to give463 mg (yield: 62%) of2-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]thiophene as a darkpurple crystal (mp: 90° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.96 (6H, t, J=8 Hz), 1.35 (4H, m), 1.57 (4H,m), 3.27 (4H, t, J=7 Hz), 3.86 (6H, s), 5.84 (2H, s), 6.92 (2H, d, J=2Hz), 7.03 (1H, d, J=2 Hz), 7.26 (1H, d, J=16 Hz), 7.48 (1H, d, J=16 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.3, 29.5, 50.7, 54.4, 88.5, 103.1,120.3, 121.9, 123.2, 127.2, 146.5, 148.5, 159.7

(53-4)5-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]thiophene-2-carbaldehyde

In a stream of argon, in 10 ml of tetrahydrofuran was dissolved 0.75 g(2.00 mmol) of 2-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]thiophene,and 1.27 ml of n-butyllithium (1.6 M solution in hexane) (2.03 mmol) wasadded dropwise thereto under cooling. The mixture was stirred for hour.To this mixture, 0.20 ml (1.20 mmol) of N,N-dimethylformamide was addeddropwise and reacted. The temperature was then allowed to risegradually, and the mixture was allowed to react at room temperature for12 hours. After the mixture was poured into 100 ml of ice water,extraction with 200 ml of chloroform, washing with a saturated salinesolution, drying over anhydrous magnesium sulfate, and concentrationwere performed. The residue was purified by silica gel chromatography togive 482 mg (yield: 60%) of5-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]thiophene-2-carboaldehydeas a dark purple crystal (mp: 105-106° C.).

¹H-NMR (600 MHz, CDCl₃) δ: 0.96 (6H, t, J=8 Hz), 1.36 (4H, m), 1.59 (4H,m), 3.26 (4H, t, J=7 Hz), 3.84 (6H, s), 5.79 (2H, s), 6.97 (1H, d, J=4Hz), 7.46 (1H, d, J=16 Hz), 7.55 (1H, d, J=4 Hz), 7.60 (1H, d, J=16 Hz),9.73 (1H, s)

¹³C-NMR (130 MHz, CDCl₃) δ: 13.9, 20.3, 29.6, 50.8, 55.4, 88.1, 101.6,102.0, 118.4, 123.8, 125.6, 137.8, 139.0, 149.6, 157.7, 160.5, 182.1

(53-5)2-[3-cyano-5,5-dimethyl-4-[2-[5-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]-2-thienyl]vinyl]-2(5H)-furanylidene]propanedinitrile

To 20 ml of acetonitrile were added 401 mg (1.00 mmol) of5-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]thiophene-2-carbaldehyde,199 mg (1.00 mmol) of2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile, and acatalytic amount of ammonium acetate. The mixture was stirred overnight.After the reaction, the mixture was concentrated. The residue waspurified by silica gel column chromatography to give 280 mg (yield: 48%)of the target compound2-[3-cyano-5,5-dimethyl-4-(2-[5-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]-2-thienyl]vinyl)-2(5H)-furanylidene]propanedinitrileas a dark red crystal (mp: 230° C.)

¹H-NMR (600 MHz, CDCl₃) δ: 0.99 (6H, t, J=8 Hz), 1.39 (4H, m), 1.63 (4H,m), 1.72 (6H, s), 3.35 (4H, t, J=7 Hz), 3.91 (6H, s), 5.80 (2H, s), 6.48(1H, d, J=17 Hz), 6.96 (1H, d, J=4 Hz), 7.31 (1H, d, J=4 Hz), 7.49 (1H,d, J=16 Hz), 7.62 (2H, d, J=16 Hz), 7.70 (1H, d, J=17 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 19.2, 20.3, 29.7, 51.0, 54.8, 88.0,92.7, 103.2, 109.1, 111.2, 111.9, 118.0, 121.3, 123.2, 127.1, 129.7,137.4, 140.6, 151.1, 161.1, 161.8, 162.8, 175.5

Example 54

2-[3-cyano-5-methyl-5-trifluoromethyl-4-(2-[5-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]-2-thienyl]vinyl)-2(5H)-furanylidene]propanedinitrile(a black crystal; 280 mg; yield: 40%; mp: 203° C.) was synthesized inthe same manner as in Example 53.

¹H-NMR (600 MHz, CDCl₃) δ: 0.92 (6H, t, J=8 Hz), 1.33 (4H, m), 1.57 (4H,m), 1.82 (3H, s), 3.30 (4H, t, J=7 Hz), 3.84 (6H, s), 5.77 (2H, s), 6.27(1H, d, J=15 Hz), 6.96 (1H, d, J=4 Hz), 7.32 (1H, d, J=4 Hz), 7.47 (1H,d, J=15 Hz), 7.67 (1H, d, J=15 Hz), 7.99 (1H, d, J=15 Hz)

¹³C-NMR (150 MHz, THF-d₈) δ: 14.3, 18.6, 21.0, 30.6, 51.4, 55.8, 89.1,104.1, 110.3, 111.4, 112.0, 112.1, 119.0, 127.8, 129.5, 138.3, 141.7,141.9, 152.0, 162.0, 162.2, 176.3

Example 552-[3-cyano-5-phenyl-5-trifluoromethyl-4-[2-[5-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]-2-thienyl]vinyl]-2(5H)-furanylidene]propanedinitrile(a dark red crystal; 550 mg; yield: 77%; mp: 229-230° C.) wassynthesized in the same manner as in Example 53.

¹H-NMR (600 MHz, CDCl₃) δ: 0.99 (6H, t, J=8 Hz), 1.40 (4H, m), 1.63 (4H,m), 3.35 (4H, t, J=7 Hz), 3.93 (6H, s), 5.80 (2H, s), 6.52 (1H, d, J=15Hz), 6.98 (1H, d, J=4 Hz), 7.26 (1H, d, J=4 Hz), 7.49-7.52 (6H, m), 7.72(2H, d, J=15 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.1, 20.3, 29.8, 51.1, 55.6, 56.2, 88.0,103.6, 110.5, 111.2, 111.5, 111.6, 118.2, 123.0, 127.2, 127.5, 129.8,130.3, 130.5, 131.2, 137.0, 141.2, 151.2, 161.0, 161.3, 163.0, 175.4

Example 562-(4-{2-[5-(2-{2-benzyloxy-4-[(2-hydroxyethyl)-methylamino]-phenyl}-vinyl)-thiophene-2-yl]-vinyl}-3-cyano-5-phenyl-5-trifluoromethyl-5H-furan-2-ylidene)malononitrile(56-1) 2,2-dimethylpropionic acid 2-[(3-methoxyphenyl)methylamino]ethylester

In a NaOMe (15.8 g, 0.29 mol)/methanol (70 ml) solution,3-methoxyphenylamine (6.0 g, 48.7 mmol) was dissolved. The mixture wasadded to formaldehyde (2.2 g, 73.8 mmol)/methanol (25 ml) and stirred atroom temperature for 12 hours. To this mixture, NaBH₄ (1.84 g, 48.6mmol) was added. The mixture was stirred for 1 hour and reacted at 80°C. for 2 hours. After an aqueous KOH solution (1 M, 200 ml) was addeddropwise, the produced oily matter was subjected to 3 times ofextraction with 50 ml of dichloromethane. Drying over Na₂SO₄ andconcentration gave crude (3-methoxyphenyl)methylamine (yield: 6.6 g(99.9%)).

Next, (3-methoxyphenyl)methylamine (6.6 g, 48.1 mmol) and ethylbromoacetate (9.8 g, 58.4 mmol) were dissolved in acetonitrile (50 ml),and NaHCO₃ (6.1 g, 73 mmol) was added thereto. After the mixture wasstirred at 90° C. for 2 hours, triethylamine (4 ml) was added thereto atroom temperature. The mixture was stirred at room temperature for 16hours. After the solvent was evaporated off, the crude product wasdissolved in dichloromethane (100 ml) and washed with a saturated salinesolution 3 times. The organic layer was dried over Na₂SO₄ andconcentrated to give crude[(3-methoxyphenyl)methyl-amino]acetic acidethyl ester (yield: 7.4 g (68.8%)).

Next, NaBH₄ (3.8 g, 100 mmol) and LiBr (8.7 g, 100 mmol) were added toTHF (100 ml), and the mixture was stirred at 80° C. for 1 hour. To thismixture, [(3-methoxyphenyl)methylamino]acetic acid ethyl ester (7.4 g,33.1 mmol) dissolved in THF (20 ml) was added dropwise at roomtemperature. The mixture was stirred at 80° C. for 5 hours and furtherat room temperature for 16 hours. After the reaction solvent wasevaporated to about half, KH₂PO₄ (1 M, 200 ml) was slowly added dropwisethereto. The organic layer was extracted with dichloromethane (50 ml)times and dried over Na₂SO₄ to give crude2-[(3-methoxyphenyl)methylamino]ethanol (yield: 8.1 g).

Next, in toluene (100 ml) were added2-[(3-methoxyphenyl)methylamino]ethanol (8.1 g), pivaloyl chloride (10.8g, 89.4 mmol), and pyridine (8.5 g, 107 mmol). The mixture was stirredat room temperature for 1 hour and further at 85° C. for 2 hours. Afterpyridine hydrochloride was removed by filtration, the filtrate wasconcentrated. The product was purified by silica gel chromatography togive 2,2-dimethylpropionic acid 2-[(3-methoxyphenyl)methylamino]ethylester as a colorless oily matter (yield: 10.4 g (78.4%)). ¹H NMR (396MHz, CDCl₃): δ 7.14 (m, 1H, benzene ring), 6.36 (d, 1H, benzene ring),6.29-6.28 (m, 2H, benzene ring), 4.23 (t, 2H, CH₂), 3.78 (s, 3H, OCH₃),3.60 (t, 2H, CH₂), 2.97 (s, 3H, CH₃), 1.20 (m, 9H, t-Bu)

(56-2) 2,2-dimethylpropionic acid2-[(4-formyl-3-methoxyphenyl)methylamino]ethyl ester

POCl₃ (5.8 g, 37.7 mmol) was added to 20 ml of DMF in an ice bath. After40 minutes, 2,2-dimethylpropionic acid2-[(3-methoxyphenyl)methylamino]ethyl ester (10 g, 37.7 mmol) dissolvedin DMF (10 ml) was added dropwise. After the mixture was stirred for 16hours, an aqueous sodium acetate solution (20%, 100 ml) was addeddropwise thereto and the oily matter was subjected to extraction withethyl acetate. Washing was performed with a saturated aqueous NaHCO₃solution (100 ml) and then with a saturated saline solution (100 ml).After drying over Na₂SO₄ and concentration, the residue was purified bysilica gel chromatography to give a light yellow crystal (yield: 8.7 g(78.9%)).

¹H NMR (396 MHz, CDCl₃): δ10.16 (s, 1H, CHO), 7.71 (m, 1H, benzenering), 6.34 (m, 1H, benzene ring), 6.13 (d, 1H, benzene ring), 4.26 (t,2H, CH₂), 3.91 (s, 3H, OCH₃), 3.70 (t, 2H, CH₂), 3.10 (s, 3H, CH₃), 1.16(m, 9H, t-Bu)

(56-3) 2,2-dimethylpropionic acid2-{[3-methoxy-4-(2-thiophene-2-ylvinyl)phenyl]methylamino}ethyl ester

Thiophene-2-ylmethyl triphenylphosphonium chloride (4.4 g, 16.3 mmol)was added to THF (50 ml), and PhLi (8.6 g of 19% solution in hexane,19.6 mmol) was added dropwise thereto in an ice bath. After 20 minutes,2,2-dimethylpropionic acid2-[(4-formyl-3-methoxyphenyl)methylamino]ethyl ester (4.0 g, 13.6 mmol)dissolved in THF (15 ml) was added dropwise. The mixture was reacted for2 hours. The reaction mixture was added to 300 ml of ice water, and theoily matter was subjected to 3 times of extraction with dichloromethane(50 ml). Washing with a saturated saline solution, drying over Na₂SO₄,and concentration were performed. The residue was purified by silica gelchromatography to give a yellow oily matter (yield: 4.0 g (79.3%)).

¹H NMR (396 MHz, CDCl₃): δ 7.38-6.85 (m, 5H, thiophene, CH═CH, benzenering), 6.56 (dd, 1H, CH═CH), 6.34-6.24 (m, 2H, benzene ring), 4.22 (t,2H, CH₂), 3.82 (d, 3H, OCH₃), 3.59 (t, 2H, CH₂), 2.99 (s, 3H, CH₃), 1.14(m, 9H, t-Bu)

(56-4) 2-{[3-methoxy-4-(2-thiophene-2-ylvinyl)phenyl]methylamino}ethanol

NaOH (4.3 g, 107 mmol) was dissolved in ethanol (25 ml), and water (7ml) was added thereto. Next, 2,2-dimethylpropionic acid2-{[3-methoxy-4-(2-thiophene-2-ylvinyl)phenyl]methylamino}ethyl ester(4.0 g, 10.7 mmol) was dissolved in ethanol (8 ml) and added dropwise tothe mixture. The mixture was stirred at room temperature for 2 hours andfurther at 45° C. for 1 hour. After the solvent was evaporated off,water (100 ml) was added and the oily matter was subjected to extractionwith ethyl acetate. After 2 times of washing with water, drying overNa₂SO₄ and concentration were performed. The residue was purified bysilica gel chromatography to give a yellow oily matter (yield: 3.1 g(100%)).

¹H NMR (396 MHz, CDCl₃): δ 7.34-6.83 (m, 5H, thiophene, CH═CH, benzenering), 6.54 (dd, 1H, CH═CH), 6.33-6.23 (m, 2H, benzene ring), 3.83-3.75(m, 5H, CH₂, OCH₃), 3.45 (m, 2H, CH₂), 3.40 (d, 3H, CH₃)

(56-5)5-(2-{4-[(2-hydroxyethyl)methylamino]-2-methoxyphenyl}vinyl)thiophene-2-carbaldehyde

In DMF (8 ml) were dissolved2-{[3-methoxy-4-(2-thiophene-2-ylvinyl)phenyl]methylamino}ethanol (3.1g, 10.8 mmol) and imidazole (1.47 g, 21.6 mmol). Next,tert-butyldimethylsilyl chloride (2.4 g, 16.2 mmol) dissolved in DMF (5ml) was added dropwise to the mixture at room temperature. After themixture was stirred for 1 hour, 300 ml of water was added and the oilymatter was subjected to extraction with dichloromethane. Washing with asaturated saline solution, drying over Na₂SO₄ and concentration wereperformed. The residue was purified by silica gel chromatography to givea yellow oily matter([2-(tert-buthyldimethylsilanyloxy)ethyl][3-methoxy-4-(2-thiophene-2-ylvinyl)phenyl]methylamine)(yield: 4.3 g (98.6%)).

Next, in THF (30 ml) was dissolved[2-(tert-buthyldimethylsilanyloxy)ethyl][3-methoxy-4-(2-thiophene-2-ylvinyl)phenyl]methylamine(4.3 g, 10.7 mmol), and n-BuLi (1.57 mol/l, 10 ml, 15.7 mmol) was addeddropwise thereto at −78° C. After the mixture was stirred for 1 hour,DMF (0.95 g, 12.3 mmol) was added dropwise thereto. The mixture wasstirred for 1 hour. After the cooling bath was removed, water (10 ml)was added dropwise, and water (100 ml) was further added at 0° C. Theorganic layer was extracted with dichloromethane, washed with asaturated saline solution, dried over Na₂SO₄, and concentrated. Thecrude product was dissolved in 500 ml of toluene containing dissolvediodine (200 mg), and the mixture was stirred at room temperature for 30minutes. Washing was performed with an aqueous sodium bisulfite solution(5%) and then with water. After drying over Na₂SO₄ and concentration,the residue was purified by silica gel chromatography to give a reddishbrown crystal(5-[2-(4-{[2-(tert-buthyldimethylsilanyloxy)ethyl]methylamino}-2-methoxyphenyl)vinyl]thiophene-2-carbaldehyde)(yield: 4.0 g (87.4%)).

Next, in THF (100 ml) was dissolved5-[2-(4-{[2-(tert-buthyldimethylsilanyloxy)ethyl]methylamino}-2-methoxyphenyl)vinyl]thiophene-2-carbaldehyde(4.0 g, 9.4 mmol), and 1 N Bu₄N F (THF solution, 5 ml) was addeddropwise thereto. After stirred at room temperature for 1 hour, themixture was concentrated. The residue was purified by silica gelchromatography to give a reddish brown crystal(5-(2-{4-[(2-hydroxyethyl)methylamino]-2-methoxyphenyl}vinyl)thiophene-2-carbaldehyde)(yield: 2.25 g (75.5%)). ¹H NMR (396 MHz, CDCl₃): δ 9.80 (s, 1H, CHO),7.62 (d, 1H, thiophene), 7.40 (t, 2H, thiophene, CH═CH), 7.08 (q, 2H,benzene ring, CH═CH), 6.39 (m, 1H, benzene ring), 6.27 (m, 1H, benzenering), 3.90-3.84 (m, 5H, CH₂, OCH₃), 3.55 (t, 2H, CH₂), 3.06 (s, 3H,CH₃)

(56-6)2-(3-cyano-4-{2-[5-(2-{4-[(2-hydroxyethyl)methylamino]-2-methoxyphenyl}vinyl)thiophene-2-yl]vinyl}-5-phenyl-5-trifluoromethyl-5H-furan-2-ylidene)malononitrile

In a mixed solvent of ethanol (15 ml) and THF (5 ml) were dissolved5-(2-{4-[(2-hydroxyethyl)methylamino]-2-methoxyphenyl}vinyl)thiophene-2-carbaldehyde (0.5 g, 1.58mmol) and2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-5H-furan-2-ylidene)malononitrile(0.50 g, 1.58 mmol). The mixture was stirred at room temperature for 18hours and further at 50° C. for 3 hours. The mixture was cooled and thesolid was collected. The solid was washed with cold ethanol (40 ml) 3times to give a reddish brown crystal (yield: 0.91 g (93.8%)). ¹H NMR(270 MHz, DMSO-d₆): δ 7.75-7.61 (m, 7H, benzene ring, CH═CH), 7.51-7.26(m, 4H, thiophene, benzene ring, CH═CH), 6.55-6.39 (m, 2H, CH═CH,benzene ring), 6.26 (s, 1H, benzene ring), 3.88 (s, 3H, OCH₃), 3.59-3.51(m, 4H, CH₂), 3.06 (s, 3H, CH₃)

Example 572-(4-{2-[5-(2-{2-benzyloxy-4-[(2-hydroxyethyl)-methylamino]-phenyl}-vinyl)-thiophene-2-yl]-vinyl}-3-cyano-5-phenyl-5-trifluoromethyl-5H-furan-2-ylidene)malononitrile(57-1) 2,2-dimethylpropionic acid2-[(3-benzyloxyphenyl)methylamino]ethyl ester

In a NaOMe (16 g, 0.96 mol)/methanol (150 ml) solution,3-benzyloxyphenylamine (10.0 g, 50.2 mmol) was dissolved, and themixture was added to formaldehyde (2.04 g, 68.4 mmol)/methanol (50 ml).The mixture was stirred at room temperature for 12 hours. To thismixture, NaBH₄ (2.08 g, 55 mmol) was added. The mixture was stirred for1 hour and reacted at 80° C. for 2 hours. After an aqueous KOH solution(1 M, 200 ml) was added dropwise, the produced oily matter was subjectedto 3 times of extraction with 50 ml of dichloromethane. Drying overNa₂SO₄ and concentration gave crude (3-benzyloxyphenyl)methylamine(yield: 9.6 g (89.7%)).

In acetonitrile (50 ml) were dissolved (3-benzyloxyphenyl)methylamine(9.6 g) and ethylbromoacetate (10.1 g, 60.2 mmol), and NaHCO₃ (6.3 g,75.3 mmol) was added thereto. After the mixture was stirred at 90° C.for 2 hours, triethylamine (4 ml) was added thereto at room temperature.The mixture was stirred at room temperature for 16 hours. After thesolvent was evaporated off, the crude product was dissolved indichloromethane (100 ml) and washed with a saturated saline solution 3times. The organic layer was dried over Na₂SO₄ and concentrated to givecrude[(3-benzyloxyphenyl)methyl-amino]acetic acid ethyl ester (yield:10.8 g (80.0%)).

Next, NaBH₄ (3.8 g, 100 mmol) and LiBr (8.7 g, 100 mmol) were added toTHF (100 ml), and the mixture was stirred at 80° C. for 1 hour. To thismixture, [(3-benzyloxyphenyl)methylamino]acetic acid ethyl ester (10.8g) dissolved in THF (20 ml) was added dropwise at room temperature. Themixture was stirred at 80° C. for 5 hours and further at roomtemperature for 16 hours. After the reaction solvent was evaporated toabout half, KH₂PO₄ (1 M, 200 ml) was slowly added dropwise. The organiclayer was extracted with dichloromethane (50 ml) 3 times, dried overNa₂SO₄ and concentrated to give crude2-[(3-benzyloxyphenyl)methylamino]ethanol (yield: 10.3 g (90.4%)).

Next, to toluene (50 ml) were added2-[(3-benzyloxyphenyl)methylamino]ethanol (10.3 g, 39.9 mmol), pivaloylchloride (9.6 g, 79.8 mmol), and pyridine (7.6 g, 95.8 mmol). Themixture was stirred at room temperature for 1 hour and further at 85° C.for 2 hours. After pyridine hydrochloride was removed by filtration, thefiltrate was concentrated. The product was purified by silica gelchromatography to give 2,2-dimethylpropionic acid2-[(3-benzyloxyphenyl)methylamino]ethyl ester as a colorless oily matter(yield: 8.9 g (65.1%)).

¹H NMR (396 MHz, CDCl₃): δ 7.54 (d, 1H, benzene ring), 7.50 (d, 2H,benzene ring), 7.43 (dd, 2H, benzene ring), 7.24 (t, 1H, benzene ring),6.49-6.47 (m, 3H, benzene ring), 5.13 (s, 2H, OCH₂Ph), 4.31 (m, 2H,CH₂), 3.64 (t, 2H, CH₂), 3.00 (s, 3H, CH₃), 1.30 (s, 9H, t-Bu)

(57-2) 2,2-dimethylpropionic acid2-[(3-benzyloxy-4-formylphenyl)methylamino]ethyl ester

POCl₃ (3.6 g, 23.4 mmol) was added to 20 ml of DMF in an ice bath. After40 minutes, 2,2-dimethylpropionic acid2-[(3-benzyloxyphenyl)methylamino]ethyl ester (8.0 g, 23.4 mmol)dissolved in DMF (10 ml) was added dropwise. The mixture was stirred for16 hours. After an aqueous sodium acetate solution (20%, 100 ml) wasadded dropwise, the oily matter was subjected to extraction with ethylacetate. Washing was performed with a saturated aqueous NaHCO₃ solution(100 ml) and then with a saturated saline solution (100 ml). Afterdrying over Na₂SO₄ and concentration, the residue was purified by silicagel chromatography to give a light yellow crystal (yield: 7.2 g(83.6%)).

¹H NMR (396 Hz, CDCl₃): δ 10.28 (s, 1H, CHO), 7.73 (d, 1H, benzenering), 7.44 (d, 1H, benzene ring), 7.40 (d, 2H, benzene ring), 7.40-7.27(m, 2H, benzene ring), 6.33 (d, 1H, benzene ring), 6.19 (s, 1H, benzenering), 5.17 (s, 2H, CH₂Ph), 4.20 (t, 2H, CH₂), 3.62 (t, 2H, CH₂), 3.04(s, 3H, CH₃), 1.16 (m, 9H, t-Bu)

(57-3) 2,2-dimethylpropionic acid2-{[3-benzyloxy-4-(2-thiophene-2-ylvinyl)-phenyl]methylamino}ethyl ester

Thiophene-2-ylmethyl triphenylphosphonium chloride (9.0 g, 22.7 mmol)was added to THF (80 ml), and PhLi (12.0 g of 19% solution in hexane,27.2 mmol) was added dropwise thereto in an ice bath. After 20 minutes,2,2-dimethylpropionic acid2-[(3-benzyloxy-4-formylphenyl)methylamino]ethyl ester (7.0 g, 18.9mmol) dissolved in THF (20 ml) was added dropwise. The mixture wasreacted for 2 hours. After the reaction mixture was added to 300 ml ofice water, the oily matter was subjected to 3 times of extraction withdichloromethane (50 ml). Washing with a saturated saline solution,drying over Na₂SO₄, and concentration were performed. The residue waspurified by silica gel chromatography to give a yellow oily matter(yield: 7.15 g (84.5%)).

¹H NMR (396 MHz, CDCl₃): δ 7.48 (d, 1H, thiophene), 7.40-6.93 (m, 8H,thiophene, benzene ring, CH═CH), 6.88-6.86 (q, 1H, benzene ring), 6.59(dd, 1H, CH═CH), 6.35-6.26 (m, 2H, benzene ring), 5.11 (d, 2H, CH₂Ph),4.19 (m, 2H, CH₂), 3.55 (m, 2H, CH₂), 2.97 (s, 3H, CH₃), 1.17 (s, 9H,t-Bu)

(57-4)2-{[3-benzyloxy-4-(2-thiophene-2-ylvinyl)-phenyl]-methylamino}ethanol

NaOH (6.2 g, 156 mmol) was dissolved in ethanol (45 ml), and water (10ml) was added thereto. Next, 2,2-dimethylpropionic acid2-{[3-benzyloxy-4-(2-thiophene-2-ylvinyl)-phenyl]methylamino}ethyl ester(7.0 g, 15.6 mmol) was dissolved in THF (20 ml) and added dropwise. Themixture was stirred at room temperature for 2 hours and further at 45°C. for 1 hour. After the solvent was evaporated off, water (100 ml) wasadded and the oily matter was subjected to extraction with ethylacetate. After 2 times of washing with water, drying over Na₂SO₄ andconcentration were performed. The residue was purified by silica gelchromatography to give a yellow oily matter (yield: 5.69 g (99.8%)).

¹H NMR (396 MHz, CDCl₃): δ 7.48 (d, 1H, thiophene), 7.42-6.94 (m, 8H,thiophene, benzene ring, CH═CH), 6.89 (q, 1H, benzene ring), 6.60 (dd,1H, CH═CH), 6.41-6.33 (m, 2H, benzene ring), 5.12 (d, 2H, CH₂Ph), 3.77(m, 2H, CH₂), 3.46 (t, 2H, CH₂), 2.97 (s, 3H, CH₃)

(57-5)[3-benzyloxy-4-(2-thiophene-2-ylvinyl)-phenyl]-[2-(tert-buthyldimethylsilanyloxy)ethyl]methylamine

In DMF (15 ml) were dissolved2-{[3-benzyloxy-4-(2-thiophene-2-ylvinyl)-phenyl]-methylamino}ethanol(5.5 g, 15 mmol) and imidazole (2.0 g, 30 mmol). Next,tert-butyldimethylsilyl chloride (3.4 g, 22.5 mmol) was dissolved in DMF(10 ml) and added dropwise at room temperature. The mixture was stirredfor 1 hour. After 300 ml of water was added to the mixture, the oilymatter was subjected to extraction with dichloromethane. Washing with asaturated saline solution, drying over Na₂SO₄, and concentration wereperformed. The residue was purified by silica gel chromatography to givea yellow oily matter (yield: 6.05 g (87.2%)).

¹H NMR (396 MHz, CDCl₃): δ 7.46 (d, 1H, thiophene), 7.39-6.84 (m, 9H,thiophene, benzene ring, CH═CH), 6.58 (dd, 1H, CH═CH), 6.30-6.22 (m, 2H,benzene ring), 5.08 (d, 2H, CH₂Ph), 3.71 (t, 2H, CH₂), 3.42 (t, 2H,CH₂), 2.95 (d, 3H, CH₃), 0.86 (s, 9H, t-Bu), 0.00 (d, 6H, Si—CH₃)

(57-6)5-[2-(2-benzyloxy-4-{[2-(tert-buthyldimethylsilanyloxy)-ethyl]methylamino}phenyl)vinyl]thiophene-2-carbaldehyde

In THF (50 ml) was dissolved[3-benzyloxy-4-(2-thiophene-2-ylvinyl)-phenyl]-[2-(tert-buthyldimethylsilanyloxy)ethyl]methylamine(5.9 g, 12.8 mmol), and n-BuLi (1.57 mol/1, 12 ml, 18.9 mmol) was addeddropwise thereto at −78° C. After the mixture was stirred for 1 hour,DMF (1.1 g, 15.6 mmol) was added dropwise. The mixture was stirred for 1hour. After the cooling bath was removed, water (10 ml) was addeddropwise, and water (100 ml) was further added at 0° C. The organiclayer was extracted with dichloromethane, washed with a saturated salinesolution, dried over Na₂SO₄, and concentrated. The crude product wasdissolved in 500 ml of toluene containing dissolved iodine (200 mg), andthe mixture was stirred at room temperature for 30 minutes. Washing wasperformed with an aqueous sodium bisulfite solution (5%) and then withwater. After drying over Na₂SO₄ and concentration, the residue waspurified by silica gel chromatography to give a reddish brown crystal(yield: 5.0 g (79.8%)). ¹H NMR (396 MHz, CDCl₃): δ 9.77 (s, 1H, CHO),7.58 (d, 1H, thiophene), 7.47-7.33 (m, 7H, benzene ring, CH═CH,thiophene), 7.40 (d, 1H, CH═CH), 6.96 (d, 1H, benzene ring), 6.31 (d,1H, benzene ring), 6.21 (s, 1H, benzene ring), 5.13 (s, 2H, CH₂Ph), 3.72(t, 2H, CH₂), 3.46 (t, 2H, CH₂), 3.00 (s, 3H, CH₃), 0.87 (t, 9H, t-Bu),0.00 (m, 6H, Si—CH₃)

(57-7)5-(2-{2-benzyloxy-4-[(2-hydroxyethyl)-methylamino]-phenyl}-vinyl)-thiophene-2-carbaldehyde

In THF (100 ml) was dissolved5-[2-(2-benzyloxy-4-{[2-(tert-buthyldimethylsilanyloxy)ethyl]methylamino}phenyl)vinyl]thiophene-2-carbaldehyde(2.9 g, 5.9 mmol), and n-Bu₄NF (a THF solution, 5 ml) was added dropwisethereto. The mixture was stirred at room temperature for 1 hour andconcentrated. The residue was purified by silica gel chromatography togive a reddish brown crystal (yield: 2.16 g (93.5%)).

¹H NMR (396 MHz, CDCl₃): δ 9.77 (s, 1H, CHO), 7.60 (d, 1H, thiophene),7.46 (d, 2H, benzene ring), 7.43-7.39 (t, 3H, benzene ring, CH═CH),7.37-7.32 (m, 2H, benzene ring), 7.13 (d, 1H, CH═CH), 6.98 (d, 1H,thiophene), 6.39-6.29 (m, 2H, benzene ring), 5.15 (s, 2H, CH₂Ph), 3.77(t, 2H, CH₂), 3.49 (s, 2H, CH₂)/3.00 (s, 3H, CH₃)

(57-8)2-(4-{2-[5-(2-{2-benzyloxy-4-[(2-hydroxyethyl)methylamino]phenyl}vinyl]thiophene-2-yl]vinyl}-3-cyano-5-phenyl-5-trifluoromethyl-5H-furan-2-ylidene)malononitrile

In a mixed solvent of ethanol (40 ml) and THF (10 ml) were dissolved5-(2-{2-benzyloxy-4-[(2-hydroxyethyl)-methylamino]-phenyl}-vinyl]-thiophene-2-carbaldehyde(2.16 g, 5.49 mmol) and2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-5H-furan-2-ylidene)malononitrile(1.73 g, 5.49 mmol). The mixture was stirred at room temperature for 18hours and further at 50° C. for 3 hours. The mixture was cooled and thesolid was collected. The solid was washed with cold ethanol (40 ml) 3times to give a reddish brown crystal (yield: 3.72 g (98.2%)).

¹H NMR (270 MHz, CDCl₃): δ 7.52-7.35 (m, 12H, benzene ring, thiophene,CH═CH), 7.47 (dd, 2H, CH═CH), 6.92 (d, 1H, thiophene), 6.58 (dd, 2H,CH═CH), 6.38 (d, 1H, benzene ring), 6.28 (m, 1H, benzene ring), 5.19 (s,2H, CH₂Ph), 3.78 (t, 2H, CH₂), 3.52 (t, 2H, CH₂), 3.05 (s, 3H, CH₃)

Example 58 2-[3-cyano-4-[2-(8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-yl)vinyl]-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 5 ml of ethanol were dissolved 150 mg (0.65 mmol) of8-methoxy-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizine-9-carboaldehydeand 142 mg (0.71 mmol) of2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile. Themixture was stirred at room temperature for 3 hours and further at 50°C. for 3 hours. The precipitate was separated by filtration and washedwith methanol. The crystal was purified by silica gel columnchromatography and washed with methanol to give 228 mg of a dark bluecrystal having amp of 250-252° C. (yield: 85.2%). ¹H-NMR (600 MHz,CDCl₃) δ: 1.74 (6H, s), 1.94-2.01 (4H, m), 2.74-2.77 (4H, m), 3.36-3.39(4H, m), 3.76 (3H, s), 6.70 (1H, d, J=15.9 Hz), 7.24 (1H, s), 7.94 (1H,d, J=15.9 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 20.5, 21.0, 21.2, 24.4, 27.0, 27.4, 50.1,50.5, 53.0, 61.9, 91.9, 96.3, 107.5, 112.1, 112.5, 113.3, 113.7, 114.8,119.3, 126.5, 143.2, 149.7, 159.1, 174.4, 176.6

Example 592-[4-[2-[2-(tert-butyldiphenylsiloxy)-4-dibutylaminophenyl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 5 ml of ethanol were dissolved 200 mg (0.41 mmol) of2-(tert-butyldiphenylsiloxy)-4-dibutylaminobenzaldehyde and mg (0.45mmol) of 2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile.After the mixture was stirred with heating at 60° C. for 3 hours, theprecipitate was separated by filtration and washed with methanol. Thecrystal was purified by silica gel column chromatography and washed withmethanol to give 199 mg of a dark brown crystal having a mp of 220-221°C. (yield: 72.6%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.75 (6H, t, J=7.1 Hz), 0.99-1.03 (4H, m),1.14 (13H, m), 1.79 (6H, s), 2.87 (4H, br), 5.64 (1H, s), 6.29 (1H, d,J=9.3 Hz), 6.88 (1H, d, J=15.9 Hz), 7.40-7.42 (4H, m), 7.46-7.49 (2H,m), 7.66 (1H, d, J=9.3 Hz), 7.71-7.73 (4H, m), 8.15 (1H, d, J=15.9 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.7, 19.5, 20.2, 26.5, 27.2, 29.2, 51.0,53.4, 93.4, 96.2, 102.2, 107.6, 111.6, 112.4, 113.2, 113.7, 128.2,129.3, 130.5, 131.4, 135.2, 142.0, 153.5, 158.7, 174.5, 176.4

Example 602-[5-[2-(2-benzyloxy-4-dibutylaminophenyl)vinyl]thiophene-2-yl]-3-cyano-2-butenedinitrile

In 3 ml of N,N-dimethylformamide, 0.13 g (1.01 mmol) oftetracyanoethylene was dissolved. With stirring under ice cooling, 0.4 g(0.95 mmol) of [3-benzyloxy-4-[2-(thiophene-2-yl)vinyl]phenyl]dibutylamine was dissolved in 1 ml of N,N-dimethylformamide and added dropwise.The mixture was stirred for 40 minutes and further stirred with heatingat 40° C. overnight. After the reaction mixture was poured into 100 mlof water, extraction with chloroform, washing with a saturated salinesolution, drying over anhydrous sodium sulfate, and concentration wereperformed. The residue was purified by silica gel column chromatographyand washed with ethanol to give 157 mg of a black crystal having a mp of125-130° C. (yield: 31.7%). ¹H-NMR (600 MHz, CDCl₃) δ: 0.95 (6H, t,J=7.7 Hz), 1.29-1.35 (4H, m), 1.50-1.55 (4H, m), 3.27 (4H, t, J=7.7 Hz),5.21 (2H, s), 6.08 (1H, d, J=2.2 Hz), 6.29 (1H, dd, J=2.2 Hz, 8.8 Hz),7.03 (1H, d, J=4.4 Hz), 7.18 (1H, d, J=15.9 Hz), 7.34-7.37 (1H, m), 7.36(1H, d, J=8.8 Hz), 7.41-7.46 (4H, m), 7.60 (1H, d, J=15.9 Hz), 7.85 (1H,d, J=4.4 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.3, 29.5, 51.0, 70.4, 75.4, 95.8,105.6, 112.6, 113.3, 113.4, 113.8, 115.0, 126.1, 126.9, 128.2, 128.8,129.4, 130.9, 131.3, 135.2, 136.7, 141.7, 151.6, 159.7, 162.7

Example 61 2-cyano-3-(4-dibutylamino-2-methoxyphenyl)-2-butenedinitrile(61-1) Dibutyl(3-methoxyphenyl)amine

In 70 ml of 1-methyl-2-pyrrolidone were dissolved 10.0 g (45.18 mmol) of3-(dibutylamino)phenol and 12.8 g (90.18 mmol) of methyl iodide. To thismixture was added 18.7 g (135.3 mmol) of anhydrous potassium carbonateand the mixture was stirred with heating at 60° C. for 6 hours. Afterthe reaction mixture was poured into 350 ml of water, extraction withethyl acetate, washing with a saturated saline solution, drying overanhydrous sodium sulfate, and concentration were performed. The residuewas purified by silica gel column chromatography to give 5.2 g of acolorless oily matter (yield: 48.7%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.94 (6H, t, J=7.1 Hz), 1.31-1.37 (4H, m),1.55-1.59 (4H, m), 3.24 (4H, t, J=7.7 Hz), 3.78 (3H, s), 6.18-6.21 (2H,m), 6.27 (1H, dd, J=2.2 Hz, 8.8 Hz), 7.09-7.12 (1H, m)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.4, 50.8, 55.0, 98.3, 99.6,105.0, 129.8, 149.6, 160.8

(61-2) 2-cyano-3-(4-dibutylamino-2-methoxyphenyl)-2-butenedinitrile

In 8 ml of N,N-dimethylformamide, 0.5 g (3.9 mmol) of tetracyanoethylenewas dissolved. With stirring under ice cooling, 0.8 g (3.4 mmol) ofdibutyl(3-methoxyphenyl)amine was dissolved in 2 ml ofN,N-dimethylformamide and added dropwise. The mixture was stirred for 35minutes. After the ice bath was removed, the mixture was further stirredfor 2 hours. After the reaction mixture was poured into 100 ml of water,extraction with chloroform, washing with a saturated saline solution,drying over anhydrous sodium sulfate, and concentration were performed.The residue was purified by silica gel column chromatography and washedwith hexane to give 0.88 g of a black crystal having a mp of 86° C.(yield: 77.2%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.99 (6H, t, J=7.1 Hz), 1.37-1.43 (4H, m),1.61-1.66 (4H, m), 3.40 (4H, t, J=7.7 Hz), 3.94 (3H, s), 6.04 (1H, d,J=2.2 Hz), 6.34 (1H, dd, J=2.2 Hz, 9.3 Hz), 7.61 (1H, d, J=9.3 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.3, 29.6, 51.4, 55.0, 81.7, 93.4,106.2, 108.3, 113.8, 114.1, 115.0, 133.6, 135.4, 155.3, 161.4

Example 622-cyano-3-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]-2-butenedinitrile

In 7 ml of N,N-dimethylformamide, 235 mg (1.83 mmol) oftetracyanoethylene was dissolved. With stirring under ice cooling, 600mg (1.75 mmol) ofdibutyl[3-methoxy-4-[2-(thiophene-2-yl)vinyl]phenyl]amine was dissolvedin 2 ml of N,N-dimethylformamide and added dropwise. The mixture wasstirred for 1.5 hours. After the ice bath was removed, the mixture wasstirred at room temperature for 1 hour and further stirred with heatingat 50° C. overnight. After the reaction mixture was poured into 80 ml ofwater, extraction with chloroform, washing with a saturated salinesolution, drying over anhydrous sodium sulfate, and concentration wereperformed. The residue was purified by silica gel column chromatographyand washed with methanol to give 324 mg of a dark reddish crystal havinga mp of 189-192° C. (yield: 41.8%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.99 (6H, t, J=7.7 Hz), 1.36-1.42 (4H, m),1.60-1.66 (4H, m), 3.36 (4H, t, J=7.7 Hz), 3.92 (3H, s), 6.09 (1H, d,J=2.2 Hz), 6.29 (1H, dd, J=2.2 Hz, 8.8 Hz), 7.11 (1H, d, J=4.4 Hz), 7.12(1H, d, J=15.9 Hz), 7.36 (1H, d, J=8.8 Hz), 7.55 (1H, d, J=15.4 Hz),7.44 (1H, d, J=4.4 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 20.3, 29.6, 51.0, 55.2, 76.8, 93.8,105.4, 112.3, 113.3, 113.5, 113.9, 114.6, 126.0, 129.2, 130.6, 131.4,135.0, 141.6, 151.9, 160.6, 162.7

Example 632-[4-[cyano-(4-dibutylamino-2-methoxyphenyl)methylene]-2,5-cyclohexadienylidene]malonnitrile

In 8 ml of N,N-dimethylformamide, 460 mg (2.25 mmol) of7,7,8,8-tetracyanoquinodimethane was dissolved. With stirring under icecooling, 500 mg (2.12 mmol) of dibutyl(3-methoxyphenyl)amine wasdissolved in 2 ml of N,N-dimethylformamide and added dropwise. Themixture was stirred for 1.5 hours. After the ice bath was removed, themixture was further stirred for 3.5 hours. After the reaction mixturewas poured into 100 ml of water, extraction with ethyl acetate, washingwith a saturated saline solution, drying over anhydrous sodium sulfate,and concentration were performed. The residue was purified by silica gelcolumn chromatography and washed with chloroform to give 226 mg of anoff-white crystal having a mp of 215-238° C. (yield: 25.6%).

¹H-NMR (600 MHz, acetone-d₆) δ: 0.95 (6H, t, J=7.7 Hz), 1.34-1.41 (4H,m), 1.57-1.62 (4H, m), 3.36 (4H, t, J=7.7 Hz), 3.86 (3H, s), 6.24 (1H,dd, J=2.2 Hz, 8.8 Hz), 6.36 (1H, d, J=2.2 Hz), 6.71 (1H, d, J=8.8 Hz),6.96 (2H, d, J=8.2 Hz), 7.15 (2H, d, J=8.2 Hz)

¹³C-NMR (150 MHz, acetone-d₆) δ: 14.2, 20.8, 43.0, 51.3, 56.0, 96.7,104.6, 109.2, 116.9, 119.4, 120.2, 126.1, 127.5, 129.4, 145.8, 151.9,158.8

Example 642-[4-[cyano-[5-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]thiophene-2-yl]methylene]-2,5-cyclohexadienylidene]malonnitrile

In 8 ml of N,N-dimethylformamide, 375 mg (1.84 mmol) of7,7,8,8-tetracyanoquinodimethane was dissolved. With stirring under icecooling, 600 mg (1.75 mmol) ofdibutyl[3-methoxy-4-[2-(thiophene-2-yl)vinyl]phenyl]amine was dissolvedin 2 ml of N,N-dimethylformamide and added dropwise. The mixture wasstirred for 1 hour and further stirred with heating at 50° C. overnight.After the reaction mixture was poured into 80 ml of water, extractionwith ethyl acetate, washing with a saturated saline solution, dryingover anhydrous sodium sulfate and concentration were performed. Theresidue was purified by silica gel column chromatography and washed withchloroform to give 132 mg of a yellowish white crystal having a mp of211-214° C. (yield: 14.5%).

¹H-NMR (600 MHz, acetone-d₆) δ: 0.96 (6H, t, J=7.7 Hz), 1.37-1.42 (4H,m), 1.58-1.63 (4H, m), 3.37 (4H, t, J=7.7 Hz), 3.85 (3H, s), 6.24 (1H,d, J=2.2 Hz), 6.30 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.94 (1H, d, J=3.8 Hz),7.11 (2H, d, J=8.8 Hz), 7.10 (1H, d, J=16.5 Hz), 7.14 (1H, d, J=16.5Hz), 7.19 (1H, d, J=3.8 Hz), 7.25 (2H, d, J=8.8 Hz), 7.38 (1H, d, J=8.8Hz)

¹³C-NMR (150 MHz, acetone-d₆) δ: 14.3, 20.9, 43.2, 51.3, 55.5, 95.5,105.4, 111.3, 115.9, 116.7, 119.6, 119.7, 124.5, 125.5, 126.8, 127.0,129.0, 129.5, 134.5, 147.3, 149.6, 150.7, 159.7

Example 652-[2-(4-dibutylamino-2-methoxybenzylidene)-3-dicyanomethyleneindan-1-ylidene]malonnitrile

In 10 ml of anhydrous acetic acid were dissolved 0.8 g (3.04 mmol) of4-(dibutylamino)-2-methoxybenzaldehyde and 0.73 g (3.01 mmol) of1,3-bis(dicyanomethylidene)indan. The mixture was stirred with heatingat 80° C. for 2 hours. The reaction mixture was poured into 200 ml ofwater and the precipitate was separated by filtration, washed withwater, and dried. The crystal was purified by silica gel columnchromatography and washed with methanol to give 1.27 g of a blackcrystal having a mp of 195-198° C. (yield: 86.4%).

¹H-NMR (600 MHz, CDCl₃) δ: 1.01 (6H, t, J=7.7 Hz), 1.39-1.45 (4H, m),1.65-1.71 (4H, m), 3.45 (4H, t, J=7.7 Hz), 3.97 (3H, s), 6.02 (1H, d,J=1.6 Hz), 6.40 (1H, d, J=8.8 Hz), 7.40 (1H, d, J=8.8 Hz), 7.63-7.65(2H, m), 8.54-8.56 (2H, m), 9.13 1H, b)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.8, 20.3, 29.7, 51.6, 55.9, 67.4, 92.9,107.9, 114.8, 115.5, 115.8, 120.5, 124.8, 133.2, 137.9, 142.2, 156.5,161.1, 164.4

Example 662-[4-[2-[5-[2-[2-benzyloxy-4-[butyl(4-hydroxybutyl)amino]phenyl]vinyl]thiophene-2-yl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile(66-1) 4-[(3-benzyloxyphenyl)butylamino]-1-butanol

In 75 ml of dioxane were dissolved 5.19 g (19.7 mmol) of3-benzyloxybromobenzene and 3.72 g (25.6 mmol) of4-butylamino-1-butanol. To this mixture was added 5.89 g (29.5 mmol) ofpotassium hexamethyldisilazide and the mixture was stirred with heatingat 100° C. for 22 hours. After the reaction mixture was poured into 200ml of water, extraction with chloroform, washing with a saturated salinesolution, drying over anhydrous sodium sulfate, and concentration wereperformed. The residue was purified by silica gel column chromatographyto give 2.22 g of a light brown oily matter (yield: 34.4%). ¹H-NMR (600MHz, CDCl₃) δ: 0.93 (3H, t, J=7.7 Hz), 1.29-1.35 (2H, m), 1.51-1.66 (6H,m), 3.22 (2H, t, J=7.7 Hz), 3.26 (2H, t, J=7.7 Hz), 3.66 (2H, t, J=6.9Hz), 5.05 (2H, s), 6.27-6.31 (3H, m), 7.11 (1H, t, J=8.2 Hz), 7.30-7.33(1H, m), 7.37-7.39 (2H, m), 7.43-7.45 (2H, m)

(66-2) 4-[(3-benzyloxyphenyl)butylamino]butyl acetate

To 10 ml of anhydrous acetic acid was added 2.7 g (8.2 mmol) of4-[(3-benzyloxyphenyl)butylamino]-1-butanol and the mixture was stirredwith heating at 80° C. for 1 hour. The reaction mixture was poured into150 ml of water and subjected to extraction with ethyl acetate. Washingwas performed with a saturated sodium bicarbonate solution and then witha saturated saline solution. Drying over anhydrous sodium sulfate andconcentration were performed. The residue was purified by silica gelcolumn chromatography to give 2.68 g of a colorless oily matter (yield:88.0%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.93 (3H, t, J=7.1 Hz), 1.29-1.35 (2H, m),1.51-1.56 (2H, m), 1.62-1.63 (4H, m), 2.04 (3H, s), 3.22 (2H, t, J=7.7Hz), 3.25 (2H, t, J=7.1 Hz), 4.07 (2H, t, J=6.0 Hz), 5.04 (2H, s),6.25-6.30 (3H, m), 7.10 (1H, dt, J=1.1 Hz, 8.2 Hz), 7.30-7.32 (1H, m),7.36-7.39 (2H, m), 7.43-7.44 (2H, m)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.01, 20.3, 21.0, 23.8, 26.2, 29.4, 50.6,50.9, 64.3, 69.9, 99.4, 101.1, 105.3, 127.5, 127.8, 128.6, 129.9, 137.5,149.4, and 160.2, 171.2

(66-3) 4-[(3-benzyloxy-4-formylphenyl)butylamino]butyl acetate

To 10 ml of N,N-dimethylformamide was added dropwise 1.11 g (7.24 mmol)of phosphoryl chloride over 8 minutes with stirring under ice cooling.After the mixture was stirred for hour, 2.67 g (7.23 mmol) of4-[(3-benzyloxyphenyl) butylamino]butyl acetate dissolved in 4 ml ofN,N-dimethylformamide was added dropwise thereto. After stirred for 1hour, the mixture was gradually heated and stirred at 50° C. for 3 hoursand further at 70° C. for 0.5 hours. To this mixture, 20 ml of a 20%sodium acetate solution was added dropwise under cooling in an ice bath.The mixture was stirred for 1 hour and subjected to extraction withethyl acetate. Washing was performed with a saturated sodium bicarbonatesolution and then with a saturated saline solution. Drying overanhydrous sodium sulfate and concentration were performed. The residuewas purified by silica gel column chromatography to give 2.14 g of ayellow oily matter (yield: 74.7%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.94 (3H, t, J=7.7 Hz), 1.29-1.35 (2H, m),1.49-1.54 (2H, m), 1.58-1.64 (4H, m), 2.05 (3H, s), 3.26 (2H, t, J=7.7Hz), 3.31 (2H, t, J=7.7 Hz), 4.07 (2H, t, J=6.0 Hz), 5.18 (2H, s), 6.01(1H, d, J=2.2 Hz), 6.25 (1H, dd, J=2.2 Hz, 8.8 Hz), 7.33 (1H, t, J=7.1Hz), 7.38-7.44 (4H, m), 7.73 (1H, d, J=8.8 Hz), 10.25 (1H, s)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.7, 20.0, 20.7, 23.6, 25.9, 29.1, 50.4,50.7, 63.7, 69.9, 94.3, 104.5, 114.4, 126.6, 127.8, 128.5, 130.1, 136.5,153.6, 162.9, 170.8, 186.9

(66-4) 2-benzyloxy-4-[butyl(4-hydroxybutyl)amino]benzaldehyde

In 10 ml of ethanol was dissolved 2.14 g (5.38 mmol) of4-[(3-benzyloxy-4-formylphenyl)butylamino]butyl acetate. To this mixturewas added 8 ml of a 10% sodium hydroxide solution and the mixture wasstirred at room temperature for 30 minutes. After the reaction mixturewas poured into 100 ml of water, extraction with chloroform, washingwith a saturated saline solution, drying over anhydrous sodium sulfate,and concentration were performed. The residual liquid was purified bysilica gel column chromatography to give 1.63 g of a yellow liquid(yield: 85.2%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.94 (3H, t, J=7.7 Hz), 1.29-1.35 (2H, m),1.50-1.66 (6H, m), 3.27 (2H, t, J=7.7 Hz), 3.32 (2H, t, J=7.7 Hz), 3.66(2H, t, J=6.0 Hz), 5.18 (2H, s), 6.03 (1H, d, J=2.2 Hz), 6.26 (1H, dd,J=2.2 Hz, 8.8 Hz), 7.31-7.43 (6H, m), 7.72 (1H, d, J=8.8 Hz), 10.24 (1H,s)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 23.8, 29.5, 30.0, 51.0, 51.1,62.5, 70.2, 94.6, 104.8, 114.6, 127.0, 128.1, 128.8, 130.4, 136.9,154.16, 163.3, 187.2

(66-5) 2-benzyloxy-4-[butyl[4-(tert-butyldiphenylsiloxy)butyl]amino]benzaldehyde

In 20 ml of N,N-dimethylformamide were dissolved 1.63 g (4.59 mmol) of2-benzyloxy-4-[butyl(4-hydroxybutyl)amino]benzaldehyde and 1.2 g (17.63mmol) of imidazole. To this mixture, 1.27 g (4.62 mmol) oftert-butylchlorodiphenylsilane was added dropwise with stirring at roomtemperature. The mixture was stirred for 2 hours. After the reactionmixture was poured into water, extraction with ethyl acetate, washingwith a saturated saline solution, and drying over anhydrous sodiumsulfate were performed. The residue was purified by silica gel columnchromatography to give 2.08 g of a colorless oily matter (yield: 76.5%).

(66-6) [3-benzyloxy-4-(2-thiophene-2-ylvinyl)phenyl]butyl[4-(tert-butyldiphenylsiloxy)butyl]amine

In a stream of argon, to 20 ml of tetrahydrofuran was added 1.7 g ofphenyllithium (19% solution in dibutylether) (3.83 mmol), and 1.38 g(3.49 mmol) of 2-thenyl triphenylphosphonium chloride was added theretounder ice cooling over 5 minutes. After the mixture was stirred for 10minutes, 2.07 g (3.49 mmol) of2-benzyloxy-4-[butyl[4-(tert-butyldiphenylsiloxy)butyl]amino]benzaldehydedissolved in 50 ml of tetrahydrofuran was added dropwise thereto over 8minutes. The mixture was stirred under ice cooling for 2 hours. Afterthe reaction mixture was poured into water, extraction with ethylacetate, washing with a saturated saline solution, drying over anhydroussodium sulfate, and concentration were performed. The residue waspurified by silica gel column chromatography to give 2.03 g of a lightbrown oily matter (yield: 86.4%).

(66-7) 5-[2-[2-benzyloxy-4-[butyl[4-(tert-butyldiphenylsiloxy)butyl]amino]phenyl]vinyl]thiophene-2-carboaldehyde

In a stream of argon, in 20 ml of tetrahydrofuran was dissolved 2.02 g(3.0 mmol) of[3-benzyloxy-4-(2-thiophene-2-ylvinyl)phenyl]butyl[4-(tert-butyldiphenylsiloxy)butyl]amine, and 2.8 ml of n-butyllithium (1.6 mol solution in hexane)(4.48 mmol) was added dropwise thereto under cooling at −66 to −72° C.After the mixture was stirred for 35 minutes, 0.3 ml (3.9 mmol) ofN,N-dimethylformamide was added dropwise thereto. After the mixture wasstirred for 1.5 hours, the bath was removed and the temperature wasallowed to rise. At −10° C., 10 ml of water was added dropwise. Afterthe reaction mixture was poured into 100 ml of water, extraction withethyl acetate, washing with a saturated saline solution, drying overanhydrous sodium sulfate, and concentration were performed. The residualliquid was purified by silica gel column chromatography to give areddish orange oily matter. Next, 1.43 g of the oily matter wasdissolved in 150 ml of ether and 50 mg of iodine was added thereto.After stirred at room temperature for 30 minutes, the mixture was washedwith a 5% sodium bisulfite solution and then with a saturated salinesolution. Drying over anhydrous magnesium sulfate and concentration wereperformed. The residue was purified by silica gel column chromatographyto give 1.21 g of a red oily matter (yield: 57.6%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.93 (3H, t, J=7.7 Hz), 1.04 (9H, s),1.26-1.31 (2H, m), 1.47-1.55 (4H, m), 1.60-1.64 (2H, m), 3.21 (2H, t,J=7.7 Hz), 3.24 (2H, t, J=7.7 Hz), 3.67 (2H, t, J=6.0 Hz), 5.13 (2H, s),6.10 (1H, d, J=2.2 Hz), 6.25 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.98 (1H, d,J=3.8 Hz), 7.10 (1H, d, J=15.9 Hz), 7.29-7.43 (12H, m), 7.46 (1H, d,J=15.9 Hz), 7.60 (1H, d, J=3.8 Hz), 7.65-7.66 (4H, m), 9.79 (1H, s)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 19.2, 20.3, 23.9, 26.9, 29.5, 30.0,50.9, 51.0, 63.6, 70.4, 96.5, 105.0, 112.8, 116.3, 124.4, 127.0, 127.7,127.9, 128.7, 128.9, 129.3, 129.6, 133.9, 135.6, 137.2, 137.7, 139.7,149.8, 155.7, 158.3, 182.3

(66-8)5-[2-[2-benzyloxy-4-[butyl(4-hydroxybutyl)amino]phenyl]vinyl]thiophene-2-carboaldehyde

In 10 ml of tetrahydrofuran was dissolved 1.2 g (1.71 mmol) of5-[2-[2-benzyloxy-4-[butyl[4-(tert-butyldiphenylsiloxy)butyl]amino]phenyl]vinyl]thiophene-2-carboaldehyde. To this mixture, 7.6ml of tetrabutylammonium fluoride (1 mol/L solution in tetrahydrofuran)(7.6 mmol) was added dropwise with stirring at room temperature. Themixture was stirred for 1.5 hours. After the reaction mixture was pouredinto water, extraction with ethyl acetate, washing with a saturatedsaline solution, drying over anhydrous sodium sulfate, and concentrationwere performed. The residual liquid was purified by silica gel columnchromatography to give 554 mg of a red crystal (yield: 70.1%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.93 (3H, t, J=7.7 Hz), 1.28-1.34 (2H, m),1.48-1.63 (6H, m), 3.24 (2H, t, J=7.7 Hz), 3.28 (2H, t, J=7.7 Hz), 3.65(2H, t, J=6.0 Hz), 5.17 (2H, s), 6.13 (1H, d, J=2.2 Hz), 6.27 (1H, dd,J=2.2 Hz, 8.8 Hz), 6.98 (1H, d, J=3.8 Hz), 7.12 (1H, d, J=15.9 Hz),7.32-7.48 (7H, m), 7.60 (1H, d, J=3.8 Hz), 9.79 (1H, s)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 23.8, 29.5, 30.1, 50.9, 51.0,62.6, 70.4, 96.6, 105.1, 113.0, 116.4, 124.5, 127.0, 127.9, 128.7,128.9, 129.2, 137.2, 137.7, 139.7, 149.8, 155.7, 158.3, 182.3

(66-9)2-[4-[2-[5-[2-[2-benzyloxy-4-[butyl(4-hydroxybutyl)amino]phenyl]vinyl]thiophene-2-yl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In 7 ml of ethanol and 2 ml of tetrahydrofuran were dissolved 218 mg(0.47 mmol) of5-[2-[2-benzyloxy-4-[butyl(4-hydroxybutyl)amino]phenyl]vinyl]thiophene-2-carboaldehydeand 103 mg (0.52 mmol) of2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile. To thismixture was added 40 mg (0.52 mmol) of ammonium acetate, and the mixturewas stirred at room temperature for 90 minutes. The precipitate wasseparated by filtration, purified by silica gel column chromatographyand washed with methanol to give 171 mg of a dark brown crystal having amp of 216-217° C. (yield: 56.4%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.94 (3H, t, J=7.7 Hz), 1.28-1.34 (2H, m),1.48-1.64 (6H, m), 1.73 (6H, s), 3.26 (2H, t, J=7.7 Hz), 3.30 (2H, t,J=7.7 Hz), 3.66 (2H, t, J=6.0 Hz), 5.21 (2H, s), 6.12 (1H, d, J=2.2 Hz),6.29 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.50 (1H, d, J=15.4 Hz), 6.94 (1H, d,J=4.4 Hz), 7.14 (1H, d, J=15.9 Hz), 7.31 (1H, d, J=4.4 Hz), 7.34-7.49(7H, m), 7.75 (1H, d, J=15.4 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 23.8, 26.6, 29.5, 30.0, 50.9,51.0, 55.3, 62.6, 70.4, 95.2, 96.4, 96.8, 105.3, 111.1, 111.3, 111.7,112.5, 112.9, 116.2, 126.6, 126.9, 128.0, 128.7, 129.4, 130.9, 137.0,137.1, 138.0, 139.4, 150.4, 156.4, 158.7, 172.8, 175.9

Example 672-[4-[2-[5-[2-[2-benzyloxy-4-[butyl(4-hydroxybutyl)amino]phenyl]vinyl]thiophene-2-yl]vinyl]-3-cyano-5-methyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 8 ml of ethanol were dissolved 180 mg (0.39 mmol) of5-[2-[2-benzyloxy-4-[butyl(4-hydroxybutyl)amino]phenyl]vinyl]thiophene-2-carboaldehydeand 108 mg (0.43 mmol) of2-(3-cyano-4,5-dimethyl-5-trifluoromethyl-2(5H)-furanylidene)propanedinitrile.The mixture was stirred with heating at 50° C. for 3 hours. Theprecipitate was separated by filtration, purified by silica gel columnchromatography and washed with methanol to give 200 mg of a dark browncrystal having a mp of 176-178° C. (yield: 73.8%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.94 (3H, t, J=7.1 Hz), 1.28-1.34 (2H, m),1.49-1.66 (6H, m), 1.88 (3H, s), 3.27 (2H, t, J=7.7 Hz), 3.32 (2H, t,J=7.1 Hz), 3.66 (2H, t, J=6.0 Hz), 5.22 (2H, s), 6.12 (1H, s), 6.30 (1H,d, J=8.8 Hz), 6.40 (1H, d, J=15.4 Hz), 6.99 (1H, d, J=3.8 Hz), 7.17 (1H,d, J=15.4 Hz), 7.35-7.47 (7H, m), 7.54 (1H, d, J=15.4 Hz), 8.12 (1H, d,J=15.4 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.9, 19.3, 20.3, 23.9, 29.5, 30.0, 50.99,51.04, 57.2, 62.5, 70.4, 93.3, 93.5, 94.6, 96.2, 105.5, 109.9, 110.9,111.4, 112.9, 116.1, 122.1, 127.0, 127.4, 128.1, 128.7, 130.0, 132.6,137.0, 137.8, 140.3, 141.1, 150.9, 159.2, 159.4, 161.6, 175.4

Example 682-[4-[2-[5-[2-[2-benzyloxy-4-[butyl(4-hydroxybutyl)amino]phenyl]vinyl]thiophene-2-yl]vinyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

In 8 ml of ethanol were dissolved 155 mg (0.33 mmol) of5-[2-[2-benzyloxy-4-[butyl(4-hydroxybutyl)amino]phenyl]vinyl]thiophene-2-carboaldehydeand 116 mg (0.37 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile.The mixture was stirred with heating at 65° C. for 1 hour. The tar-likematter was separated by decantation, purified by silica gel columnchromatography, crystallized in methanol, and separated by filtration togive 153 mg of a dark brown crystal having amp of 181-183° C. (yield:60.2%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.93 (3H, t, J=7.1 Hz), 1.29-1.34 (2H, m),1.48-1.64 (6H, m), 3.26 (2H, t, J=7.7 Hz), 3.31 (2H, t, J=7.1 Hz), 3.66(2H, t, J=6.0 Hz), 5.21 (2H, s), 6.11 (1H, s), 6.28 (1H, d, J=8.8 Hz),6.55 (1H, d, J=14.9 Hz), 6.94 (1H, d, J=3.8 Hz), 7.14 (1H, d, J=15.9Hz), 7.20 (1H, d, J=3.8 Hz), 7.33-7.56 (12H, m), 7.78 (1H, d, J=14.9 Hz)¹³C-NMR (150 MHz, CDCl₃) S: 13.9, 20.3, 23.8, 29.5, 30.0, 51.0, 57.5,62.5, 70.4, 96.2, 105.5, 110.9, 111.1, 111.2, 111.3, 113.0, 116.2,122.3, 126.8, 126.9, 127.4, 128.1, 128.7, 129.7, 129.8, 129.9, 131.5,132.6, 137.0, 137.8, 140.1, 141.6150.8, 159.2, 159.5, 161.7, 175.5

Example 692-[4-[3-[2-butyl-3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]-1-propenyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile(69-1) 2-butyl-3,5,5-trimethyl-2-cyclohexenone

In 60 ml of 1-methyl-2-pyrrolidone were dissolved 10.0 g (72.36 mmol) ofisophorone and 14.9 g (95.6 mmol) of 1-bromobutane. To this mixture wasadded 8.1 g (144.4 mmol) of powdered potassium hydroxide and the mixturewas stirred with heating at 70° C. for 6 hours. After the reactionmixture was added to water, extraction with ethyl acetate, washing witha saturated saline solution, drying over anhydrous sodium sulfate, andconcentration were performed. The residual liquid was purified by silicagel column chromatography to give 6.31 g of a yellow oily matter (yield:44.9%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.90 (3H, t, J=7.1 Hz), 1.00 (6H, s),1.25-1.35 (4H, m), 1.91 (3H, s), 2.21 (2H, s), 2.23 (2H, s), 2.28 (2H,t, J=7.7 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 21.3, 22.9, 24.8, 28.2, 31.4, 32.7,47.0, 51.4, 134.8, 152.3, 199.0

(69-2)3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-butyl-5,5-dimethyl-2-cyclohexenone

0.3 g (13.0 mmol) of sodium was dissolved in 15 ml of ethanol. Next,2.63 g (10.0 mmol) of 4-dibutylamino-2-methoxybenzaldehyde and 2.22 g(11.0 mmol) of 2-butyl-3,5,5-trimethyl-2-cyclohexenone were dissolved in5 ml of ethanol and added to the mixture. To this mixture, 0.36 g ofammonium acetate was added and the mixture was stirred with heating at60° C. for 22 hours. To the mixture, 100 ml of ethyl acetate was added.Washing with a saturated saline solution, drying over anhydrous sodiumsulfate, and concentration were performed. The residual liquid waspurified by silica gel column chromatography to give 465 mg of a darkred oily matter (yield: 10.6%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.93 (3H, t, J=6.6 Hz), 0.97 (6H, t, J=7.7Hz), 1.05 (6H, s), 1.33-1.40 (8H, m), 1.58-1.63 (4H, m), 2.29 (2H, s),2.51 (2H, s), 2.51-2.53 (2H, m), 3.31 (4H, t, J=7.7 Hz), 3.87 (3H, s),6.13 (1H, d, J=2.2 Hz), 6.28 (1H, dd, J=2.2 Hz, 8.8 Hz), 7.20 (1H, d,J=15.9 Hz), 7.24 (1H, d, J=15.9 Hz), 7.41 (1H, d, J=8.8 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 14.1, 20.4, 23.0, 24.3, 28.5, 29.5,32.2, 32.4, 39.9, 50.8, 51.6, 55.3, 94.4, 104.7, 113.4, 122.0, 128.3,129.6, 133.7, 149.0, 150.0, 159.0, 199.3

(69-3) [2-butyl-3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]acetonitrile

In a stream of argon, 3.8 ml of lithium diisopropylamide (2 mol/Lsolution) was added to 2 ml of tetrahydrofuran and cooled in a dryice/acetone bath. To this mixture, 0.31 g (7.55 mmol) of acetonitrile in4 ml of tetrahydrofuran was added dropwise. To this mixture was addeddropwise3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-2-butyl-5,5-dimethyl-2-cyclohexenonein 5 ml of tetrahydrofuran. The mixture was stirred for 30 minutes andthe temperature was allowed to rise slowly. At 0° C., 10 ml of water wasadded dropwise. The organic solvent was evaporated off in a reducedpressure. Extraction with ethyl acetate, washing with a saturated salinesolution, drying over anhydrous sodium sulfate, and concentration gave areddish orange oily matter. This oily matter was dissolved in 4 ml ofacetic acid and stirred with heating at 75° C. for 2 hours. After themixture was cooled, 100 ml of dichloromethane was added thereto andneutralized with a saturated sodium bicarbonate solution. The organiclayer was separated, dried over anhydrous magnesium sulfate, andconcentrated. The residue was purified by silica gel columnchromatography to give 158 mg of an orange crystal (yield: 39.3%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.96 (3H, t, J=6.6 Hz), 0.97 (6H, t, J=7.7Hz), 1.00 (6H, s), 1.33-1.43 (8H, m), 1.55-1.62 (4H, m), 2.38 (2H, s),2.44 (2H, t, J=7.7 Hz), 2.50 (2H, s), 3.30 (4H, t, J=7.7 Hz), 3.86 (3H,s), 6.13 (1H, d, J=2.2 Hz), 6.27 (1H, dd, J=2.2 Hz, 8.8 Hz), 7.09 (1H,d, J=15.9 Hz), 7.15 (1H, d, J=15.9 Hz), 7.36 (1H, d, J=8.8 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.4, 23.1, 26.9, 27.7, 28.1, 29.5,30.4, 31.7, 40.4, 43.6, 50.9, 55.3, 89.5, 94.6, 104.7, 113.8, 119.7,122.2, 127.7, 128.0, 130.6, 140.4, 149.7, 158.7, 159.3

(69-4) [2-butyl-3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]acetaldehyde

In 5 ml of toluene was dissolved 158 mg (0.34 mmol) of[2-butyl-3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]acetonitrile.The mixture was cooled in a dry ice/acetone bath in a stream of argon.To this mixture, 0.46 ml of diisobutylaluminum hydride (1.5 mol solutionin toluene) (0.69 mmol) was added dropwise. The mixture was stirred for1.5 hours and the temperature was allowed to rise. At 0° C., 5 ml of a5% ammonium chloride solution was added dropwise. After the mixture wasstirred for 30 minutes, the phases were separated and the water phasewas washed with ethyl acetate. The organic layer was washed with asaturated saline solution, dried over anhydrous sodium sulfate, andconcentrated. The residual liquid was purified by silica gel columnchromatography to give 119 mg of a red oily matter (yield: 74.8%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.95 (3H, t, J=7.1 Hz), 0.97 (6H, t, J=7.7Hz), 1.02 (6H, s), 1.34-1.44 (8H, m), 1.56-1.63 (4H, m), 2.42 (2H, s),2.51 (2H, t, J=7.4 Hz), 2.69 (2H, s), 3.31 (4H, t, J=7.7 Hz), 3.87 (3H,s), 6.13 (1H, d, J=2.2 Hz), 6.19 (1H, d, J=8.2 Hz), 6.28 (1H, dd, J=2.2Hz, 8.8 Hz), 7.11 (1H, d, J=15.9 Hz), 7.23 (1H, d, J=15.9 Hz), 7.38 (1H,d, J=8.8 Hz), 10.13 (1H, d, J=8.2 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.4, 23.2, 27.2, 28.3, 29.6, 30.3,32.0, 39.6, 40.4, 50.9, 55.3, 60.4, 94.5, 104.7, 113.9, 122.7, 123.2,127.9, 128.1, 132.6, 141.9, 149.7, 158.1, 158.8, 191.8

(69-5) 2-[4-[3-[2-butyl-3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]-1-propenyl]-3-cyano-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrile

118 mg (0.25 mmol) of[2-butyl-3-[2-(4-dibutylamino-2-methoxyphenyl)vinyl]-5,5-dimethyl-2-cyclohexenylidene]acetaldehydeand 90 mg (0.29 mmol) of2-(3-cyano-4-methyl-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene]propanedinitrilewere dissolved, and the mixture was stirred with heating at 50° C. for40 minutes. The solvent was evaporated off. The residue was purified bysilica gel column chromatography and washed with methanol to give 133 mgof a black crystal having a mp of 109-113° C. (yield: 68.9%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.88 (3H, s), 0.97-1.00 (12H, m), 1.34-1.47(8H, m), 1.59-1.64 (4H, m), 2.17 (1H, d, J=15.4 Hz), 2.28 (1H, d, J=15.9Hz), 2.47 (2H, s), 2.25 (2H, b), 3.35 (4H, t, J=7.7 Hz), 3.89 (3H, s),6.09 (1H, d, J=2.2 Hz), 6.30 (1H, dd, J=2.2 Hz, 8.8 Hz), 6.37 (1H, d,J=13.7 Hz), 6.58 (1H, d, J=12.6 Hz), 7.32 (1H, d, J=15.9 Hz), 7.40 (1H,d, J=15.9 Hz), 7.41 (1H, d, J=8.8 Hz), 7.51-7.54 (5H, m), 8.00 (1H, b)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0 14.1, 20.3, 23.2, 27.0, 27.8, 28.5,29.6, 30.7, 32.2, 40.6, 40.8, 55.3, 94.0, 95.2, 105.4, 111.6, 112.1,114.1, 115.1, 121.3, 122.2, 123.2, 124.9, 126.9, 129.5, 130.8, 131.0,133.5, 135.6, 147.5, 150.7, 151.3, 159.5, 160.2, 161.3, 176.0

Example 702-{3-cyano-4-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]-5-methyl-5-trifluoromethyl-2(5H)-furanylidene}propanedinitrile

The compound was synthesized in the same procedure as in Example 30.

¹H-NMR (600 MHz, CDCl₃) δ: 1.00 (6H, t, J=7.7 Hz), 1.42 (4H, m), 1.68(4H, m), 1.86 (3H, s), 3.44 (4H, m), 3.92 (6H, s), 5.76 (2H, s), 7.17(1H, d, J=10.4 Hz), 8.70 (1H, d, J=10.4 Hz) ¹³C-NMR (150 MHz, CDCl₃) δ:13.8, 20.2, 27.2, 29.6, 51.2, 55.7, 87.8, 96.1, 104.0, 110.0, 112.1,113.2, 114.1, 131.6, 14.07, 154.5, 163.4, 176.6, 176.9

Example 712-{3-cyano-4-[2-(4-dibutylamino-2,6-dimethoxyphenyl)vinyl]-5-phenyl-5-trifluoromethyl-2(5H)-furanylidene}propanedinitrile

The compound was synthesized in the same procedure as in Example 30.

¹H-NMR (600 MHz, CDCl₃) δ: 0.98 (6H, t, J=7.7 Hz), 1.39 (4H, m), 1.64(4H, m), 3.41 (4H, t, 7.7 Hz), 3.83 (6H, s), 5.69 (2H, s), 7.31 (1H, b),7.46-7.48 (3H, m), 7.52-7.53 (2H, m), 8.42 (1H, b)

¹³C-NMR (150 MHz, CDCl₃) δ: 13.8, 20.1, 29.7, 51.4, 55.7, 88.0, 105.3,106.4, 110.8, 112.1, 113.0, 126.7, 129.1, 130.6, 131.5, 144.0, 155.9,164.3, 177.0, 183.6

Comparative Example 12-[4-[2-[5-[2-(4-dibutylaminophenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

(1-1) Dibutyl[4-[2-(thiophene-2-yl)vinyl]phenyl]amine

In a stream of argon, to 70 ml of tetrahydrofuran was added 10.45 g ofphenyllithium (19% solution in dibutylether) (23.6 mmol), and 8.09 g(20.5 mmol) of 2-thenyl triphenylphosphonium chloride was added theretounder cooling. To this mixture was added dropwise 4.92 g (21.0 mmol) of4-(dibutylamino)benzaldehyde. The mixture was stirred at the sametemperature for 1 hour. After the reaction mixture was poured intowater, extraction with toluene, washing with a saturated salinesolution, drying over anhydrous sodium sulfate, and concentration wereperformed. The residue was purified by silica gel column chromatographyto give an orange liquid. This liquid was dissolved in 200 ml of tolueneand 200 mg of iodine was added thereto. After stirred at roomtemperature for 15 minutes, the mixture was added to water and thephases were separated. The organic layer was dried over anhydrous sodiumsulfate and concentrated. The residue was purified by silica gel columnchromatography to give 6.09 g of an orange oily matter (yield: 94.8%).

¹H NMR (600 MHz, CDCl₃) S: 0.96 (6H, t, J=7.7 Hz), 1.32-1.39 (4H, m),1.55-1.60 (4H, m), 3.28 (4H, t, J=7.7 Hz), 6.60 (2H, d, J=8.8 Hz), 6.84(1H, d, J=15.9 Hz), 6.95 (1H, d, J=3.9 Hz), 6.96 (1H, d, J=3.9 Hz), 6.99(1H, d, J=15.9 Hz), 7.09 (1H, t, J=3.0 Hz), 7.31 (2H, d, J=8.8 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.5, 50.8, 116.9, 128.8, 111.7,122.7, 124.1, 124.2, 127.4 127.6, 128.8, 144.2, 147.8

(1-2) 5-[2-[4-(dibutylamino)phenyl]vinyl]thiophene-2-carboaldehyde

In a stream of argon, in tetrahydrofuran was dissolved 3.0 g (0.97 mmol)of dibutyl[4-[2-(thiophene-2-yl)vinyl]phenyl]amine. To this mixture, 9.0ml of n-butyllithium (1.6 M solution in hexane) (14.4 mmol) was addeddropwise under cooling. After the mixture was stirred for 1 hour, 0.87 g(11.9 mmol) of N,N-dimethylformamide was added dropwise thereto. After20 minutes, the temperature was allowed to rise and 30 ml of water wasadded dropwise. Tetrahydrofuran was evaporated off. Extraction withchloroform, drying over anhydrous sodium sulfate, and concentration wereperformed. The residual liquid was purified by silica gel columnchromatography to give 3.12 g of a reddish orange oily matter (yield:95.5%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.96 (6H, t, J=7.7 Hz), 1.33-1.39 (4H, m),1.55-1.61 (4H, m), 3.30 (4H, t, J=7.7 Hz), 6.61 (2H, d, J=8.8 Hz), 6.96(1H, d, J=15.9 Hz), 7.07 (1H, d, J=15.9 Hz), 7.03 (1H, d, J=4.2 Hz),7.35 (2H, d, J=8.8 Hz), 7.61 (1H, t, J=4.2 Hz), 9.81 (1H, s)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.4, 50.7, 115.5, 133.7, 111.5,122.8, 124.7, 128.5, 137.6, 140.0, 148.7, 154.5, 182.2

(1-3)2-[4-[2-[5-[2-(4-dibutylaminophenyl)vinyl]thiophene-2-yl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In an ethanol/tetrahydrofuran mixed solvent were dissolved 170 mg (0.50mmol) of 5-[2-[4-(dibutylamino)phenyl]vinyl]thiophene-2-carboaldehydeand 110 mg (0.55 mmol) of 2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene)propanedinitrile. To this mixture, 42 mg of ammonium acetate was added,and the mixture was stirred at room temperature. The solvent wasevaporated off. The residue was purified by silica gel columnchromatography and washed with ethanol to give 198 mg of a black crystalhaving amp of 208-209° C. (yield: 76.1%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.1 Hz), 1.34-1.40 (4H, m),1.57-1.62 (4H, m), 1.75 (6H, s), 3.32 (4H, t, J=7.7 Hz), 6.55 (1H, d,J=15.9 Hz), 6.63 (2H, d, J=8.8 Hz), 6.98 (1H, d, J=15.9 Hz), 7.02 (1H,d, J=3.8 Hz), 7.08 (1H, d, J=15.9 Hz), 7.36 (1H, d, J=3.8 Hz), 7.37 (2H,d, J=8.8 Hz), 7.77 (1H, d, J=15.9 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 26.6, 29.5, 50.8, 55.8, 95.8,96.9, 111.1, 111.5, 111.7, 112.3, 115.3, 122.7, 126.7, 129.0, 135.1,137.2, 137.8, 139.4, 149.2, 154.8, 172.9, 175.8

Comparative Example 22-[4-[2-[4-[2-(4-dibutylaminophenyl)vinyl]phenyl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

(2-1) 4-[2-[4-(dibutylamino)phenyl]vinyl]benzyl alcohol

In a stream of argon, to 40 ml of tetrahydrofuran was added 8.0 g ofphenyllithium (19% solution in dibutylether) (18.1 mmol). To thismixture, 3.81 g (8.2 mmol) of4-(hydroxymethyl)benzyltriphenylphosphonium bromide was added undercooling. After the mixture was stirred at the same temperature, 2.0 g(8.6 mmol) of 4-(dibutylamino)benzaldehyde was added thereto. Themixture was stirred at the same temperature for 1 hour. After thereaction mixture was added to water, extraction with toluene, washingwith a saturated saline solution, and drying over anhydrous sodiumsulfate were performed. Toluene was evaporated off. The residue waspurified by silica gel column chromatography to give 2.37 g of a yellowliquid (yield: 85.5%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.96 (6H, t, J=7.7 Hz), 1.33-1.39 (4H, m),1.55-1.60 (4H, m), 3.28 (4H, t, J=7.7 Hz), 4.66 (2H, d, J=4.9 Hz), 6.62(2H, d, J=8.8 Hz), 6.86 (1H, d, J=16.5 Hz), 7.02 (1H, d, J=16.5 Hz),7.31 (2H, d, J=8.3 Hz), 7.37 (2H, d, J=8.8 Hz), 7.45 (2H, d, J=8.3 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.5, 50.8, 65.3, 111.6, 123.2,124.1, 126.1, 127.4, 127.7, 129.0, 138.0, 139.2, 148.0

(2-2) 4-[2-[4-(dibutylamino)phenyl]vinyl]benzaldehyde

In 30 ml of dichloromethane was suspended 6.0 g (69.0 mmol) of activemanganese dioxide. Next, 1.17 g (3.45 mmol) of4-[2-[4-(dibutylamino)phenyl]vinyl]benzyl alcohol was dissolved indichloromethane and added to the suspension. After stirred at roomtemperature for 20 hours, the suspension was filtrated and the solventwas evaporated off. The residue was purified by silica gel column,chromatography to give 0.74 g of a yellow crystal (yield: 64.1%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.7 Hz), 1.34-1.40 (4H, m),1.56-1.62 (4H, m), 3.30 (4H, t, J=7.7 Hz), 6.63 (2H, d, J=8.2 Hz), 6.89(1H, d, J=15.9 Hz), 7.19 (1H, d, J=15.9 Hz), 7.40 (2H, d, J=8.8 Hz),7.59 (2H, d, J=8.3 Hz), 7.82 (2H, d, J=8.3 Hz), 9.95 (1H, s)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 29.5, 50.8, 111.6, 122.0, 123.5,126.1, 128.4, 130.2, 132.7, 134.4, 144.8, 148.5, 191.6

(2-3)2-[4-[2-[4-[2-(4-dibutylaminophenyl)vinyl]phenyl]vinyl]-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile

In an ethanol/tetrahydrofuran mixed solvent were dissolved 180 mg (0.54mmol) of 4-[2-(4-dibutylaminophenyl)vinyl]benzaldehyde and 118 mg (0.59mmol) of 2-(3-cyano-4,5,5-trimethyl-2(5H)-furanylidene]propanedinitrile.To this mixture, 46 mg (0.60 mmol) of ammonium acetate was added, andthe mixture was stirred at room temperature. The solvent was evaporatedoff. The residue was purified by silica gel column chromatography andwashed with ethanol to give 245 mg of a black crystal having a mp of224-226° C. (yield: 88.4%).

¹H-NMR (600 MHz, CDCl₃) δ: 0.97 (6H, t, J=7.1 Hz), 1.34-1.41 (4H, m),1.57-1.62 (4H, m), 1.80 (6H, s), 3.31 (4H, t, J=7.7 Hz), 6.63 (2H, d,J=8.8 Hz), 6.88 (1H, d, J=15.9 Hz), 7.00 (1H, d, J=16.5 Hz), 7.21 (1H,d, J=16.5 Hz), 7.41 (2H, d, J=8.8 Hz), 7.54 (2H, d, J=8.8 Hz), 7.59 (2H,d, J=8.8 Hz), 7.61 (1H, d, J=15.9 Hz)

¹³C-NMR (150 MHz, CDCl₃) δ: 14.0, 20.3, 26.6, 29.5, 50.8, 57.2, 97.4,98.7, 110.5, 111.1, 111.6, 111.9, 113.3, 121.7, 123.5, 126.7, 128.7,129.8, 131.6, 132.9, 134.8, 147.1, 148.7, 173.7, 175.5

Test Example 1

The initial decomposition temperature (Td), maximum absorbance spectrum(λ_(max)), and hyperpolarizability (β) of each of the compounds obtainedin Examples 1 to 15 and Comparative Examples 1 and 2 were measured asdescribed below. The results are shown in Tables 6 and 7.

Measurement of Initial Decomposition Temperature (Td)

The initial decomposition temperature (Td) was measured with athermogravimetry-differential thermal analysis apparatus TG8120 (RigakuCorporation) under the following conditions: test sample, 5 mg; standardsample, Al₂O₃; nitrogen atmosphere; and heating rate, 10° C./min.

Measurement of Hyperpolarizability (β)

The hyperpolarizability (β) was measured in the same manner as themethod described in the following reference: “Intermolecular CouplingEnhancement of the Molecular Hyperpolarizability in MultichromophoricDipolar Dendrons”, Shiyoshi Yokoyama, Tatsuo Nakahama, Akira Otomo, andShinro Mashiko, Journal of the American Chemical Society, vol. 122,pages 3174-3181 (2000). The laser light source was an erbium-doped fiberlaser (Aisin Seiki Co., Ltd.)(Femtolite C-40-SP, BS-60; wavelength: 1.56μm; pulse duration: 100 fsec; repetition rate: 50 MHz; and output: 60mW). The photodetector was a photomultiplier tube (R3896) (HamamatsuPhotonics K.K.). Each of the nonlinear optical compounds was adjusted toa concentration of 5 μmol/l in 1,4-dioxane and used as the test sample.The hyperpolarizability (βr) of the nonlinear optical compound wasdetermined by irradiating a laser beam, detecting the generated secondharmonic wave intensity with the photomultiplier tube, and comparing thehyperpolarizability with that of a reference sample, according to themethod described in the reference. The hyperpolarizability of thereference sample was the hyperpolarizability of chloroform (−0.49×10⁻³⁰esu) as the solvent or the hyperpolarizability of the nonlinear opticalcompound (No. 5b) described in the following reference: “PyrrolineChromophores for Electro-Optics”, Sei-Hum Jang, Jingdong Luo, Neil M.Tucker, Amalia Leclercq, Egbert Zojer, Marnie A. Haller, Tae-Dong Kim,Jae-Wook Kang, Kimberly Firestone, Denise Bale, David Lao, Jason B.Benedict, Dawn Cohen, Werner Kaminsky, Bart Kahr, Jean-Juc Bredas,Philip Reid, Larry R. Dalton, and Alex K.-Y. Jen, Chemistry ofMaterials, 18(13), pages 2982-2988 (2006). Measurement of MaximumAbsorption Wavelength (λmax)

Each of the nonlinear optical compounds was adjusted to a concentrationof 5 μmol/l in 1,4-dioxane, and the maximum absorption wavelength (max)of the nonlinear optical compound was measured with aultraviolet-visible spectroscopy (UVmini-1240) (Shimadzu Corporation).

TABLE 6 T_(d) λ_(max) β (° C.) (nm) ×10⁻³⁰ (esu) β_(r) Comparative 257.7610 2179 1 Example 1 Example 1 247.0 643 7256 3.3 Example 2 199.2 71011309 5.2 Example 3 206.5 726 12181 5.6 Example 4 252.6 644 7539 3.5Example 5 193.7 713 11876 5.5 Example 6 219.8 727 10916 4.8 Example 13283.3 648 8389 3.9 Example 14 261.2 716 11875 5.5 Example 15 230.3 73110437 4.8 (β_(r) is the ratio to the hyperpolarizability of ComparativeExample 1.)

TABLE 7 T_(d) λ_(max) β (° C.) (nm) ×10⁻³⁰ (esu) β_(r) Comparative 258.4550 653 1 Example 2 Example 7 271.1 573 1216 1.9 Example 8 255.7 6292694 4.1 Example 9 235.9 637 2609 4.0 Example 10 261.1 576 1654 2.5Example 11 256.5 637 3656 5.6 Example 12 232.3 644 3394 5.2 (β_(r) isthe ratio to the hyperpolarizability of Comparative Example 2.)

As is apparent from Tables 6 and 7, the initial decompositiontemperatures (Td) of the nonlinear optical compounds (Examples 1 to 15)of the present invention are not significantly different from those ofthe nonlinear optical compounds of Comparative Examples 1 and 2.However, it was shown that the nonlinear optical compounds (Examples 1to 15) of the present invention have a markedly improvedhyperpolarizability (β) in comparison with the nonlinear opticalcompounds of Comparative Examples 1 and 2.

These test results revealed that, in comparison with the nonlinearoptical compounds of Comparative Examples 1 and 2, the nonlinear opticalcompounds of the present invention have a far superior nonlinear opticalproperty that has been improved without significantly deterioration ofthe heat resistance.

Test Example 2

The initial decomposition temperature (Td), maximum absorbance spectrum(λmax), and hyperpolarizability (β) of each of the compounds obtained inExamples 1 to 6, 13 to 18, 27-1 to 27-28, 28 to 30, and 35 to 57 andComparative Example 1 were measured as described below. The results areshown in Table 8.

Measurement of Initial Decomposition Temperature (Td)

The initial decomposition temperature (Td) was measured with athermogravimetry-differential thermal analysis apparatus TG8120 (RigakuCorporation) under the following conditions: test sample, 5 mg; standardsample, Al₂O₃; nitrogen atmosphere; and heating rate, 10° C./min.

Measurement of Hyperpolarizabilities (β)

Measurement of the hyperpolarizability (β) and calculation of thenonresonant hyperpolarizability (β₀) were performed in the same manneras the method described in the following reference: “IntermolecularCoupling Enhancement of the Molecular Hyperpolarizability inMultichromophoric Dipolar Dendron”, Shiyoshi Yokoyama, Tatsuo Nakahama,Akira Otomo, and Shinro Mashiko, Journal of the American ChemicalSociety, vol. 122, pages 3174-3181 (2000). The laser light source was aNd: YAG laser OPO system (Spectra-Physics K.K.) (Quanta Ray Nd: YAGlaser, OPO versaScan; wavelength: 1.901m; pulse width: 20 nsec;repetition rate: 10 Hz; and output: 90 mW). The photodetector was aphotomultiplier tube (R2658) (Hamamatsu Photonics K.K.). Each of thenonlinear optical compounds was adjusted to a concentration of 5 μmol/lin chloroform and used as the test sample. The hyperpolarizability (β)of the nonlinear optical compound was determined by irradiating a laserbeam, detecting the generated second harmonic wave intensity with thephotomultiplier tube, and comparing the hyperpolarizability with that ofa reference sample, according to the method described in the reference.The hyperpolarizability of the reference sample was thehyperpolarizability of chloroform (−0.49×10⁻³⁰ esu) as the solvent orthe hyperpolarizability of the nonlinear optical compound (No. 5b)described in the following reference: “Pyrroline Chromophores forElectro-Optics”, Sei-Hum Jang, Jingdong Luo, Neil M. Tucker, AmaliaLeclercq, Egbert Zojer, Marnie A. Haller, Tae-Dong Kim, Jae-Wook Kang,Kimberly Firestone, Denise Bale, David Lao, Jason B. Benedict, DawnCohen, Werner Kaminsky, Bart Kahr, Jean-Juc Bredas, Philip Reid, LarryR. Dalton, and Alex K.-Y. Jen, Chemistry Materials, vol. 28, pages2982-2988 (2006). Measurement of Maximum Absorption Wavelength (λmax)

Each of the nonlinear optical compounds was adjusted to a concentrationof 10 μmol/l in chloroform, and the maximum absorption wavelength (λmax)of the nonlinear optical compound was measured with aultraviolet-visible spectroscopy (U-4000)(Hitachi, Ltd.).

TABLE 8 T_(d) λ_(max) β × 10⁻³⁰ β₀ × 10⁻³⁰ (° C.) (nm) (esu) β_(r) (esu)β_(0r) Comparative 257.7 685 1498 1 627 1   Example 1 Example 1 247.0719 2666 1.8 976 1.6 Example 2 199.2 814 9551 6.4 2073 3.3 Example 3206.5 819 10856 7.2 2270 3.6 Example 4 252.6 715 3161 2.1 1176 1.9Example 5 193.7 812 9491 6.3 2090 3.3 Example 6 219.8 823 10203 6.8 20683.3 Example 13 283.3 724 4434 3.0 1589 2.5 Example 14 261.2 826 118647.9 2348 3.7 Example 15 230.3 839 12911 8.6 2287 3.6 Example 16 187.6716 2913 1.9 1080 1.7 Example 17 256.1 824 11535 7.7 2320 3.7 Example 18231.4 836 12538 8.4 2281 3.6 Example 27-1 261.8 717 3490 2.3 1288 2.1Example 27-2 200.6 818 9906 6.6 2087 3.3 Example 27-3 215.2 829 108567.2 2096 3.3 Example 27-4 279.0 706 2589 1.7 999 1.6 Example 27-5 237.1810 8988 6.0 2008 3.2 Example 27-6 226.4 818 10461 7.0 2204 3.5 Example27-7 259.9 710 3127 2.1 1188 1.9 Example 27-8 251.3 812 8498 5.7 18713.0 Example 27-9 231.1 816 7700 5.1 1647 2.6 Example 27-10 251.3 7132943 2.0 1104 1.8 Example 27-11 224.1 813 8409 5.6 1838 2.9 Example27-12 202.4 821 8732 5.8 1798 2.9 Example 27-13 250.4 713 2262 1.5 8491.4 Example 27-14 248.4 809 7830 5.2 1762 2.8 Example 27-15 230.9 8169432 6.3 2017 3.2 Example 27-16 247.0 712 2506 1.7 944 1.5 Example 27-17183.1 814 6776 4.5 1470 2.3 Example 27-18 187.6 823 8248 5.5 1672 2.7Example 27-19 296.5 701 3259 2.2 1282 2.0 Example 27-20 258.0 806 65104.3 1496 2.4 Example 27-21 253.3 808 7041 4.7 1595 2.5 Example 27-22267.6 676 2046 1.4 882 1.4 Example 27-23 257.5 774 4743 3.2 1330 2.1Example 27-24 246.1 781 5865 3.9 1580 2.5 Example 27-25 276.1 662 14591.0 659 1.1 Example 27-26 235.4 742 4313 2.9 1425 2.3 Example 27-27208.7 756 5112 3.4 1578 2.5 Example 27-28 191.6 826 7935 5.3 1570 2.5Example 28 261.3 592 1321 0.9 730 1.2 Example 29 223.8 629 2658 1.8 13292.1 Example 30 216.5 632 3435 2.3 1702 2.7 Example 35 238.9 675 3356 2.21452 2.3 Example 36 210.6 731 2786 1.9 968 1.5 Example 37 211.0 737 34452.3 1165 1.9 Example 38 216.8 696 1962 1.3 787 1.3 Example 39 259.2 8264810 3.2 952 1.5 Example 40 205.4 833 6375 4.3 1190 1.9 Example 41 265.3721 3507 2.3 1273 2.0 Example 42 257.5 819 4778 3.2 999 1.6 Example 43235.9 830 4366 2.9 836 1.3 Example 44 251.5 717 4546 3.0 1678 2.7Example 45 245.9 830 4926 3.3 943 1.5 Example 46 238.8 747 4299 2.9 13872.2 Example 47 204.4 919 17572 11.7 — — Example 48 216.4 927 21311 14.2— — Example 49 262.2 750 5254 3.5 1670 2.7 Example 50 188.5 928 114327.6 — — Example 51 211.8 933 11386 7.6 — — Example 52 257.9 678 2362 1.61011 1.6 Example 53 251.3 749 4360 3.2 1553 2.5 Example 54 233.6 84010124 6.8 1777 2.8 Example 55 233.7 846 10718 7.2 1778 2.8 Example 56307 767 4374 2.9 1275 2.0 Example 57 301 767 4603 3.1 1341 2.1 (β_(r)and β_(0r) are the ratios to the hyperpolarizability and to thenonresonant hyperpolarizability of Comparative Example 1, respectively.)

As is apparent from Table 8, the initial decomposition temperatures (Td)of the nonlinear optical compounds (Examples 1 to 6, 13 to 18, 27-1 to27-28, 28 to 30, and 35 to 57) of the present invention are notsignificantly different from that of the nonlinear optical compound ofComparative Example 1. However, it was shown that the nonlinear opticalcompounds (Examples 1 to 6, 13 to 18, 27-1 to 27-28, 28 to 30, and 35 to57) of the present invention have a markedly improvedhyperpolarizabilities (β) in comparison with the nonlinear opticalcompound of Comparative Example 1.

These test results revealed that, in comparison with the nonlinearoptical compound of Comparative Example 1, the nonlinear opticalcompounds of the present invention have a far superior nonlinear opticalproperty that has been improved without significantly deterioration ofthe heat resistance.

INDUSTRIAL APPLICABILITY

By employing an aryl group substituted with a substituted oxy group inthe donor structure D, the nonlinear optical property of the nonlinearoptical compound of the present invention is improved withoutsignificant deterioration of the heat resistance. A material containingsuch a nonlinear optical compound exhibiting a larger nonlinear opticaleffect can give a nonlinear optical element that can change theintensity and phase of light in response to even a weaker external fieldapplied thereto.

When such a nonlinear optical element is used in, for example, anoptical modulator utilizing the electrooptic effect, the opticalmodulator can be driven by lower electric power, which makes possibleenergy saving and miniaturization. In addition, since the element has alarger nonlinear optical effect, which can change the intensity andphase of light in response to even a weaker electric field appliedthereto, the element can be used for an electric field sensor thatmeasures a leaked electric field of an electronic integrated circuit orfor a sensor for terahertz electromagnetic waves. Further, the elementin combination with an electronic circuit can be used for, for example,optical signal transmission between electronic circuits.

REFERENCE SIGNS LIST

1. Substrate, 2. Lower Electrode, 3. First Clad Layer, 4. Core Layer, 6.Second Clad Layer, 8. Upper Electrode, 9. Optical Waveguide Core, 10.Optical Waveguide (Nonlinear Optical Element)

1. A chromophore comprising a donor structure D, a π-conjugated bridgestructure B, and an acceptor structure A, the donor structure Dcomprising an aryl group substituted with a substituted oxy group andthe acceptor structure A being free of —SO₂—.
 2. The chromophoreaccording to claim 1, wherein the substituted oxy group is attached toan ortho-carbon atom of the aryl group or to an ortho-carbon atom andthe para-carbon atom of the aryl group.
 3. The chromophore according toclaim 1, wherein the aryl group may be further substituted with anoptionally substituted amino group.
 4. The chromophore according toclaim 1, wherein the π-conjugation of the π-conjugated bridge structureB is a carbon-carbon conjugation.
 5. The chromophore according to claim1, wherein the chromophore is represented by the formula D-B-A, whereinD represents the donor structure D, B represents the π-conjugated bridgestructure B, and A represents the acceptor structure A.
 6. Thechromophore according to claim 1, wherein the donor structure D isrepresented by the formula D-1:

wherein at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independentlyrepresents an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group; the rest independently represent ahydrogen atom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ eachmay have the same or different substituents (when R_(D) ² and R_(D) ³are each attached to adjacent carbon atoms of the aryl of the donorstructure D, (1) R_(D) ² and R_(D) ³ may form, together with the twoadjacent carbon atoms, a ring optionally having a substituent; and R_(D)¹ represents an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or (2) R_(D) ² and R_(D) ³ may form, together with the twoadjacent carbon atoms, a heterocyclic ring containing an oxygen atom asa hetero atom and optionally having a substituent); and R_(D) ⁴ andR_(D) ⁵ independently represent a hydrogen atom, an alkyl group, ahaloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or R_(D) ⁴and R_(D) ⁵ form, together with the nitrogen atom to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent; or (a) R_(D) ² and —NR_(D)⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵ independently form,together with the carbon atoms to which they are attached, aheterocyclic ring containing the nitrogen atom as a hetero atom andoptionally having a substituent.
 7. The chromophore according to claim1, wherein the donor structure D is represented by the formula D-1-1:

wherein R_(D) ¹ represents an alkoxy group, an aryloxy group, anaralkyloxy group, a silyloxy group, an alkenyloxy group, analkenylcarbonyloxy group, an alkynyloxy group, or a hydroxy group, andR_(D) ¹ may have a substituent; R_(D) ² and R_(D) ³ independentlyrepresent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxygroup, an aralkyloxy group, a silyloxy group, an alkenyloxy group, analkenylcarbonyloxy group, an alkynyloxy group, or a hydroxy group, andR_(D) ² and R_(D) ³ each may have the same or different substituents(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D, R_(D) ² and R_(D) ³ may form,together with the two adjacent carbon atoms, a ring optionally having asubstituent); and R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogenatom, an alkyl group, a haloalkyl group, a hydroxyalkyl group, anacyloxyalkyl group, a silyloxyalkyl group, an aminoalkyl group, or anaryl group, and R_(D) ⁴ and R_(D) ⁵ each may have the same or differentsubstituents, or R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogenatom to which they are attached, a heterocyclic ring containing thenitrogen atom as a hetero atom and optionally having a substituent; or(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent.
 8. The chromophore accordingto claim 1, wherein the donor structure D is represented by the formulaD-1-2:

wherein at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independentlyrepresents an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group; the rest independently represent ahydrogen atom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ eachmay have the same or different substituents (when R_(D) ² and R_(D) ³are each attached to adjacent carbon atoms of the aryl of the donorstructure D, (1) R_(D) ² and R_(D) ³ may form, together with the twoadjacent carbon atoms, a ring optionally having a substituent; and R_(D)¹ represents an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or (2) R_(D) ² and R_(D) ³ may form, together with the twoadjacent carbon atoms, a heterocyclic ring containing an oxygen atom asa hetero atom and optionally having a substituent); and R_(D) ⁴ andR_(D) ⁵ independently represent a hydrogen atom, an alkyl group, ahaloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or R_(D) ⁴and R_(D) ⁵ form, together with the nitrogen atom to which they areattached, a saturated heterocyclic ring optionally having a substituent,or R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogen atom to whichthey are attached, with the aryl carbon atom to which said nitrogen atomis attached, and with the aryl carbon atom which is adjacent to saidcarbon atom, a heterocyclic ring containing the nitrogen atom as ahetero atom and optionally having a substituent.
 9. The chromophoreaccording to claim 1, wherein the donor structure D is represented bythe formula D-2:

wherein at least one of R_(D) ¹, R_(D) ², and R_(D) ³ independentlyrepresents an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group; the rest independently represent ahydrogen atom or an alkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ eachmay have the same or different substituents (when R_(D) ² and R_(D) ³are each attached to adjacent carbon atoms of the aryl of the donorstructure D, (1) R_(D) ² and R_(D) ³ may form, together with the twoadjacent carbon atoms, a ring optionally having a substituent; and R_(D)¹ represents an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent, or (2) R_(D) ² and R_(D) ³ may form, together with the twoadjacent carbon atoms, a heterocyclic ring containing an oxygen atom asa hetero atom and optionally having a substituent).
 10. The chromophoreaccording to claim 1, wherein the donor structure D is represented bythe formula D-2-1:

wherein R_(D) ¹ represents an alkoxy group, an aryloxy group, anaralkyloxy group, a silyloxy group, an alkenyloxy group, analkenylcarbonyloxy group, an alkynyloxy group, or a hydroxy group, andR_(D) ¹ may have a substituent; and R_(D) ² and R_(D) ³ independentlyrepresent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxygroup, an aralkyloxy group, a silyloxy group, an alkenyloxy group, analkenylcarbonyloxy group, an alkynyloxy group, or a hydroxy group, andR_(D) ² and R_(D) ³ each may have the same or different substituents(when R_(D) ² and R_(D) ³ are each attached to adjacent carbon atoms ofthe aryl of the donor structure D, R_(D) ² and R_(D) ³ may form,together with the two adjacent carbon atoms, a ring optionally having asubstituent).
 11. The chromophore according to claim 1, wherein theacceptor structure A is represented by the formula selected from thegroup consisting of:

wherein Y represents —CR_(A) ¹R_(A) ²—, —O—, —S—, —SO—, —SiR_(A)'R_(A)²—, —NR— (wherein R represents a hydrogen atom or an alkyl group), or—C(═CH₂)—; and R_(A) ¹ and R_(A) ² independently represent a hydrogenatom, an alkyl group, an alkenyl group, a cycloalkyl group, acycloalkenyl group, an alkoxy group, a haloalkyl group, or an arylgroup, and R_(A) ¹ and R_(A) ² each may have the same or differentsubstituents, or R_(A) ¹ and R_(A) ² form, together with the carbon atomto which they are attached, a structure that may have a substituent andis represented by the following formula:


12. The chromophore according to claim 1, wherein the carbon-carbonconjugated bridge structure B may have a substituent and is representedby the formula selected from the group consisting of:

wherein R_(B) ¹ to R_(B) ⁸ independently represent a hydrogen atom, analkyl group, an alkoxy group, an aryl group, an alkenyl group, acycloalkyl group, a cycloalkenyl group, a haloalkyl group, an aralkylgroup, an aryloxy group, or an aralkyloxy group, and R_(B) ¹ to R_(B) ⁸each may have the same or different substituents; n represents aninteger of 1 to 5; and m and m′ independently represent an integer of 0to
 3. 13. The chromophore according to claim 1, wherein thecarbon-carbon conjugated bridge structure B is represented by theformula B-I:

wherein π¹ and π² independently represent the same or differentcarbon-carbon conjugated π-bonds, and π¹ and π² each may have the sameor different substituents; and R_(B) ¹ and R_(B) ² independentlyrepresent a hydrogen atom, an alkyl group, an alkoxy group, an arylgroup, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, ahaloalkyl group, an aralkyl group, an aryloxy group, or an aralkyloxygroup, and R_(B) ¹ and R_(B) ² each may have the same or differentsubstituents.
 14. The chromophore according to claim 1, wherein thechromophore is represented by the formula I-1:

wherein π¹ and π² independently represent the same or differentcarbon-carbon conjugated π-bonds, and π¹ and π² each may have the sameor different substituents; at least one of R_(D) ¹, R_(D) ², and R_(D) ³independently represents an alkoxy group, an aryloxy group, anaralkyloxy group, a silyloxy group, an alkenyloxy group, analkenylcarbonyloxy group, an alkynyloxy group, or a hydroxy group; therest independently represent a hydrogen atom or an alkyl group; andR_(D) ¹, R_(D) ², and R_(D) ³ each may have the same or differentsubstituents (when R_(D) ² and R_(D) ³ are each attached to adjacentcarbon atoms of the aryl of the donor structure D, (1) R_(D) ² and R_(D)³ may form, together with the two adjacent carbon atoms, a ringoptionally having a substituent; and R_(D) ¹ represents an alkoxy group,an aryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxygroup, an alkenylcarbonyloxy group, an alkynyloxy group, or a hydroxygroup, and R_(D) ¹ may have a substituent, or (2) R_(D) ² and R_(D) ³may form, together with the two adjacent carbon atoms, a heterocyclicring containing an oxygen atom as a hetero atom and optionally having asubstituent); R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogenatom, an alkyl group, a haloalkyl group, a hydroxyalkyl group, anacyloxyalkyl group, a silyloxyalkyl group, an aminoalkyl group, or anaryl group, and R_(D) ⁴ and R_(D) ⁵ each may have the same or differentsubstituents, or R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogenatom to which they are attached, a heterocyclic ring containing thenitrogen atom as a hetero atom and optionally having a substituent; or(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent; R_(B) ¹ and R_(B) ²independently represent a hydrogen atom, an alkyl group, an alkoxygroup, an aryl group, an aralkyl group, an aryloxy group, or anaralkyloxy group, and R_(B) ¹ and R_(B) ² each may have the same ordifferent substituents; and R_(A) ¹ and R_(A) ² independently representa hydrogen atom, an alkyl group, a haloalkyl group, or an aryl group,and R_(A) ¹ and R_(A) ² each may have the same or differentsubstituents.
 15. The chromophore according to claim 1, wherein thechromophore is represented by the formula I-1-1:

wherein π¹ and π² independently represent the same or differentcarbon-carbon conjugated π-bonds, and π¹ and π² each may have the sameor different substituents; R_(D) ¹ represents an alkoxy group, anaryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxygroup, an alkenylcarbonyloxy group, an alkynyloxy group, or a hydroxygroup, and R_(D) ¹ may have a substituent; R_(D) ² and R_(D) ³independently represent a hydrogen atom, an alkyl group, an alkoxygroup, an aryloxy group, an aralkyloxy group, a silyloxy group, analkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group, or ahydroxy group, and R_(D) ² and R_(D) ³ each may have the same ordifferent substituents (when R_(D) ² and R_(D) ³ are each attached toadjacent carbon atoms of the aryl of the donor structure D, R_(D) ² andR_(D) ³ may form, together with the two adjacent carbon atoms, a ringoptionally having a substituent); R_(D) ⁴ and R_(D) ⁵ independentlyrepresent a hydrogen atom, an alkyl group, a haloalkyl group, ahydroxyalkyl group, an acyloxyalkyl group, a silyloxyalkyl group, anaminoalkyl group, or an aryl group, and R_(D) ⁴ and R_(D) ⁵ each mayhave the same or different substituents, or R_(D) ⁴ and R_(D) ⁵ form,together with the nitrogen atom to which they are attached, aheterocyclic ring optionally having a substituent; or (a) R_(D) ² and—NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵ independentlyform, together with the carbon atoms to which they are attached, aheterocyclic ring containing the nitrogen atom as a hetero atom andoptionally having a substituent; R_(B) ¹ and R_(B) ² independentlyrepresent a hydrogen atom, an alkyl group, an alkoxy group, an arylgroup, an aralkyl group, an aryloxy group, or an aralkyloxy group, andR_(B) ¹ and R_(B) ² each may have the same or different substituents;and R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, analkyl group, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A)² each may have the same or different substituents.
 16. The chromophoreaccording to claim 1, wherein the chromophore is represented by theformula I-2:

wherein π¹ and π² independently represent the same or differentcarbon-carbon conjugated πbonds, and π¹ and π² each may have the same ordifferent substituents; at least one of R_(D) ¹, R_(D) ², and R_(D) ³independently represents an alkoxy group, an aryloxy group, anaralkyloxy group, a silyloxy group, an alkenyloxy group, analkenylcarbonyloxy group, an alkynyloxy group, or a hydroxy group; therest independently represent a hydrogen atom or an alkyl group; andR_(D) ¹, R_(D) ², and R_(D) ³ each may have the same or differentsubstituents (when R_(D) ² and R_(D) ³ are each attached to adjacentcarbon atoms of the aryl of the donor structure D, (1) R_(D) ² and R_(D)³ may form, together with the two adjacent carbon atoms, a ringoptionally having a substituent; and R_(D) ¹ represents an alkoxy group,an aryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxygroup, an alkenylcarbonyloxy group, an alkynyloxy group, or a hydroxygroup, and R_(D) ¹ may have a substituent, or (2) R_(D) ² and R_(D) ³may form, together with the two adjacent carbon atoms, a heterocyclicring containing an oxygen atom as a hetero atom and optionally having asubstituent); R_(B) ¹ and R_(B) ² independently represent a hydrogenatom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group,an aryloxy group, or an aralkyloxy group, and R_(B) ¹ and R_(B) ² eachmay have the same or different substituents; and R_(A) ¹ and R_(A) ²independently represent a hydrogen atom, an alkyl group, a haloalkylgroup, or an aryl group, and R_(A) ¹ and R_(A) ² each may have the sameor different substituents.
 17. The chromophore according to claim 1,wherein the carbon-carbon conjugated bridge structure B is representedby the formula B-II:

wherein π¹ and π₂ independently represent the same or differentcarbon-carbon conjugated π-bonds, and π¹ and π² each may have the sameor different substituents; and R_(B) ¹, R_(B) ², R_(B) ³, and R_(B) ⁴independently represent a hydrogen atom, an alkyl group, an alkoxygroup, an aryl group, an alkenyl group, a cycloalkyl group, acycloalkenyl group, a haloalkyl group, an aralkyl group, an aryloxygroup, or an aralkyloxy group, and R_(B) ¹, R_(B) ², R_(B) ³, and R_(B)⁴ each may have the same or different substituents.
 18. The chromophoreaccording to claim 1, wherein the chromophore is represented by theformula II-1:

wherein π¹ and π² independently represent the same or differentcarbon-carbon conjugated π-bonds, and π¹ and π² each may have the sameor different substituents; at least one of R_(D) ¹, R_(D) ², and R_(D) ³independently represents an alkoxy group, an aryloxy group, anaralkyloxy group, a silyloxy group, an alkenyloxy group, analkenylcarbonyloxy group, an alkynyloxy group, or a hydroxy group; therest independently represent a hydrogen atom or an alkyl group; andR_(D) ¹, R_(D) ², and R_(D) ³ each may have the same or differentsubstituents (when R_(D) ² and R_(D) ³ are each attached to adjacentcarbon atoms of the aryl of the donor structure D, (1) R_(D) ² and R_(D)³ may form, together with the two adjacent carbon atoms, a ringoptionally having a substituent; and R_(D) ¹ represents an alkoxy group,an aryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxygroup, an alkenylcarbonyloxy group, an alkynyloxy group, or a hydroxygroup, and R_(D) ¹ may have a substituent, or (2) R_(D) ² and R_(D) ³may form, together with the two adjacent carbon atoms, a heterocyclicring containing an oxygen atom as a hetero atom and optionally having asubstituent); R_(D) ⁴ and R_(D) ⁵ independently represent a hydrogenatom, an alkyl group, a haloalkyl group, a hydroxyalkyl group, anacyloxyalkyl group, a silyloxyalkyl group, an aminoalkyl group, or anaryl group, and R_(D) ⁴ and R_(D) ⁵ each may have the same or differentsubstituents, or R_(D) ⁴ and R_(D) ⁵ form, together with the nitrogenatom to which they are attached, a heterocyclic ring containing thenitrogen atom as a hetero atom and optionally having a substituent; or(a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵independently form, together with the carbon atoms to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent; R_(B) ¹, R_(B) ², R_(B) ³, andR_(B) ⁴ independently represent a hydrogen atom, an alkyl group, analkoxy group, an aryl group, an aralkyl group, an aryloxy group, or anaralkyloxy group, and R_(B) ¹, R_(B) ², R_(B) ³, and R_(B) ⁴ each mayhave the same or different substituents; and R_(A) ¹ and R_(A) ²independently represent a hydrogen atom, an alkyl group, a haloalkylgroup, or an aryl group, and R_(A) ¹ and R_(A) ² each may have the sameor different substituents.
 19. The chromophore according to claim 1,wherein the chromophore is represented by the formula II-1-1:

wherein π¹ and π² independently represent the same or differentcarbon-carbon conjugated π-bonds, and π¹ and π² each may have the sameor different substituents; R_(D) ¹ represents an alkoxy group, anaryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxygroup, an alkenylcarbonyloxy group, an alkynyloxy group, or a hydroxygroup, and R_(D) ¹ may have a substituent; R_(D) ² and R_(D) ³independently represent a hydrogen atom, an alkyl group, an alkoxygroup, an aryloxy group, an aralkyloxy group, a silyloxy group, analkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group, or ahydroxy group, and R_(D) ² and R_(D) ³ each may have the same ordifferent substituents (when R_(D) ² and R_(D) ³ are each attached toadjacent carbon atoms of the aryl of the donor structure D, R_(D) ² andR_(D) ³ may form, together with the two adjacent carbon atoms, a ringoptionally having a substituent); R_(D) ⁴ and R_(D) ⁵ independentlyrepresent a hydrogen atom, an alkyl group, a haloalkyl group, ahydroxyalkyl group, an acyloxyalkyl group, a silyloxyalkyl group, anaminoalkyl group, or an aryl group, and R_(D) ⁴ and R_(D) ⁵ each mayhave the same or different substituents, or R_(D) ⁴ and R_(D) ⁵ form,together with the nitrogen atom to which they are attached, aheterocyclic ring containing the nitrogen atom as a hetero atom andoptionally having a substituent; or (a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and(b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵ independently form, together with thecarbon atoms to which they are attached, a heterocyclic ring containingthe nitrogen atom as a hetero atom and optionally having a substituent;R_(B) ¹, R_(B) ², R_(B) ³, and R_(B) ⁴ independently represent ahydrogen atom, an alkyl group, an alkoxy group, an aryl group, anaralkyl group, an aryloxy group, or an aralkyloxy group, and R_(B) ¹,R_(B) ², R_(B) ³, and R_(B) ⁴ each may have the same or differentsubstituents; and R_(A) ¹ and R_(A) ² independently represent a hydrogenatom, an alkyl group, a haloalkyl group, or an aryl group, and R_(A) ¹and R_(A) ² each may have the same or different substituents.
 20. Thechromophore according to claim 1, wherein the carbon-carbon conjugatedbridge structure B is represented by the formula B-III:

wherein m and m′ independently represent an integer of 0 to 3; and R_(B)¹, R_(B) ², and R_(B) ³ independently represent a hydrogen atom, analkyl group, an alkoxy group, an aryl group, an alkenyl group, acycloalkyl group, a cycloalkenyl group, a haloalkyl group, an aralkylgroup, an aryloxy group, or an aralkyloxy group, and R_(B) ¹, R_(B) ²,and R_(B) ³ each may have the same or different substituents.
 21. Thechromophore according to claim 1, wherein the chromophore is representedby the formula III-1:

wherein m and m′ independently represent an integer of 0 to 3; at leastone of R_(D) ¹, R_(D) ², and R_(D) ³ independently represents an alkoxygroup, an aryloxy group, an aralkyloxy group, a silyloxy group, analkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group, or ahydroxy group; the rest independently represent a hydrogen atom or analkyl group; and R_(D) ¹, R_(D) ², and R_(D) ³ each may have the same ordifferent substituents (when R_(D) ² and R_(D) ³ are each attached toadjacent carbon atoms of the aryl of the donor structure D, (1) R_(D) ²and R_(D) ³ may form, together with the two adjacent carbon atoms, aring optionally having a substituent; and R_(D) ¹ represents an alkoxygroup, an aryloxy group, an aralkyloxy group, a silyloxy group, analkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group, or ahydroxy group, and R_(D) ¹ may have a substituent, or (2) R_(D) ² andR_(D) ³ may form, together with the two adjacent carbon atoms, aheterocyclic ring containing an oxygen atom as a hetero atom andoptionally having a substituent); R_(D) ⁴ and R_(D) ⁵ independentlyrepresent a hydrogen atom, an alkyl group, a haloalkyl group, ahydroxyalkyl group, an acyloxyalkyl group, a silyloxyalkyl group, anaminoalkyl group, or an aryl group, and R_(D) ⁴ and R_(D) ⁵ each mayhave the same or different substituents, or R_(D) ⁴ and R_(D) ⁵ form,together with the nitrogen atom to which they are attached, aheterocyclic ring containing the nitrogen atom as a hetero atom andoptionally having a substituent; or (a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and(b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵ independently form, together with thecarbon atoms to which they are attached, a heterocyclic ring containingthe nitrogen atom as a hetero atom and optionally having a substituent;R_(B) ¹, R_(B) ², and R_(B) ³ independently represent a hydrogen atom,an alkyl group, an alkoxy group, an aryl group, an aralkyl group, anaryloxy group, or an aralkyloxy group, and R_(B) ¹, R_(B) ², and R_(B) ³each may have the same or different substituents; and R_(A) ¹ and R_(A)² independently represent a hydrogen atom, an alkyl group, a haloalkylgroup, or an aryl group, and R_(A) ¹ and R_(A) ² each may have the sameor different substituents.
 22. The chromophore according to claim 1,wherein the chromophore is represented by the formula III-1-1:

wherein m and m′ independently represent an integer of 0 to 3; R_(D) ¹represents an alkoxy group, an aryloxy group, an aralkyloxy group, asilyloxy group, an alkenyloxy group, an alkenylcarbonyloxy group, analkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent; R_(D) ² and R_(D) ³ independently represent a hydrogenatom, an alkyl group, an alkoxy group, an aryloxy group, an aralkyloxygroup, a silyloxy group, an alkenyloxy group, an alkenylcarbonyloxygroup, an alkynyloxy group, or a hydroxy group, and R_(D) ² and R_(D) ³each may have the same or different substituents (when R_(D) ² and R_(D)³ are each attached to adjacent carbon atoms of the aryl of the donorstructure D, R_(D) ² and R_(D) ³ may form, together with the twoadjacent carbon atoms, a ring optionally having a substituent); R_(D) ⁴and R_(D) ⁵ independently represent a hydrogen atom, an alkyl group, ahaloalkyl group, a hydroxyalkyl group, an acyloxyalkyl group, asilyloxyalkyl group, an aminoalkyl group, or an aryl group, and R_(D) ⁴and R_(D) ⁵ each may have the same or different substituents, or R_(D) ⁴and R_(D) ⁵ form, together with the nitrogen atom to which they areattached, a heterocyclic ring containing the nitrogen atom as a heteroatom and optionally having a substituent; or (a) R_(D) ² and —NR_(D)⁴R_(D) ⁵ and (b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵ independently form,together with the carbon atoms to which they are attached, aheterocyclic ring containing the nitrogen atom as a hetero atom andoptionally having a substituent; R_(B) ¹, R_(B) ², and R_(B) ³independently represent a hydrogen atom, an alkyl group, an alkoxygroup, an aryl group, an aralkyl group, an aryloxy group, or anaralkyloxy group, and R_(B)', R_(B) ², and R_(B) ³ each may have thesame or different substituents; and R_(A) ¹ and R_(A) ² independentlyrepresent a hydrogen atom, an alkyl group, a haloalkyl group, or an arylgroup, and R_(A) ¹ and R_(A) ² each may have the same or differentsubstituents.
 23. The chromophore according to claim 1, wherein thecarbon-carbon conjugated bridge structure B is represented by theformula B-IV:

wherein n represents an integer of 1 to
 5. 24. The chromophore accordingto claim 1, wherein the chromophore is represented by the formulaIV-1-a:

wherein n represents an integer of 1 to 5; R_(D) ¹ represents an alkoxygroup, an aryloxy group, an aralkyloxy group, a silyloxy group, analkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group, or ahydroxy group, and R_(D) ¹ may have a substituent; R_(D) ² and R_(D) ³independently represent a hydrogen atom, an alkyl group, an alkoxygroup, an aryloxy group, an aralkyloxy group, a silyloxy group, analkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group, or ahydroxy group, and R_(D) ² and R_(D) ³ each may have the same ordifferent substituents (when R_(D) ² and R_(D) ³ are each attached toadjacent carbon atoms of the aryl of the donor structure D, R_(D) ² andR_(D) ³ may form, together with the two adjacent carbon atoms, a ringoptionally having a substituent); R_(D) ⁴ and R_(D) ⁵ independentlyrepresent a hydrogen atom, an alkyl group, a haloalkyl group, ahydroxyalkyl group, an acyloxyalkyl group, a silyloxyalkyl group, anaminoalkyl group, or an aryl group, and R_(D) ⁴ and R_(D) ⁵ each mayhave the same or different substituents, or R_(D) ⁴ and R_(D) ⁵ form,together with the nitrogen atom to which they are attached, aheterocyclic ring containing the nitrogen atom as a hetero atom andoptionally having a substituent; or (a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and(b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵ independently form, together with thecarbon atoms to which they are attached, a heterocyclic ring containingthe nitrogen atom as a hetero atom and optionally having a substituent;and R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, analkyl group, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A)² each may have the same or different substituents.
 25. The chromophoreaccording to claim 1, wherein the chromophore is represented by theformula IV-1-b:

wherein n represents an integer of 1 to 5; R_(D) ¹ represents an alkoxygroup, an aryloxy group, an aralkyloxy group, a silyloxy group, analkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group, or ahydroxy group, and R_(D) ¹ may have a substituent; R_(D) ² and R_(D) ³independently represent a hydrogen atom, an alkyl group, an alkoxygroup, an aryloxy group, an aralkyloxy group, a silyloxy group, analkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group, or ahydroxy group, and R_(D) ² and R_(D) ³ each may have the same ordifferent substituents (when R_(D) ² and R_(D) ³ are each attached toadjacent carbon atoms of the aryl of the donor structure D, R_(D) ² andR_(D) ³ may form, together with the two adjacent carbon atoms, a ringoptionally having a substituent); R_(D) ⁴ and R_(D) ⁵ independentlyrepresent a hydrogen atom, an alkyl group, a haloalkyl group, ahydroxyalkyl group, an acyloxyalkyl group, a silyloxyalkyl group, anaminoalkyl group, or an aryl group, and R_(D) ⁴ and R_(D) ⁵ each mayhave the same or different substituents, or R_(D) ⁴ and R_(D) ⁵ form,together with the nitrogen atom to which they are attached, aheterocyclic ring containing the nitrogen atom as a hetero atom andoptionally having a substituent; or (a) R_(D) ² and —NR_(D) ⁴R_(D) ⁵ and(b) R_(D) ³ and —NR_(D) ⁴R_(D) ⁵ independently form, together with thecarbon atoms to which they are attached, a heterocyclic ring containingthe nitrogen atom as a hetero atom and optionally having a substituent;and R_(A) ¹ and R_(A) ² independently represent a hydrogen atom, analkyl group, a haloalkyl group, or an aryl group, and R_(A) ¹ and R_(A)² each may have the same or different substituents.
 26. The chromophoreaccording to claim 1, wherein the chromophore is represented by theformula IV-2-a:

wherein n represents an integer of 1 to 5; at least one of R_(D) ¹,R_(D) ², and R_(D) ³ independently represents an alkoxy group, anaryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxygroup, an alkenylcarbonyloxy group, an alkynyloxy group, or a hydroxygroup; the rest independently represent a hydrogen atom or an alkylgroup; and R_(D) ¹, R_(D) ², and R_(D) ³ each may have the same ordifferent substituents (when R_(D) ² and R_(D) ³ are each attached toadjacent carbon atoms of the aryl of the donor structure D, (1) R_(D) ²and R_(D) ³ may form, together with the two adjacent carbon atoms, aring optionally having a substituent; and R_(D) ¹ represents an alkoxygroup, an aryloxy group, an aralkyloxy group, a silyloxy group, analkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group, or ahydroxy group, and R_(D) ¹ may have a substituent, or (2) R_(D) ² andR_(D) ³ may form, together with the two adjacent carbon atoms, aheterocyclic ring containing an oxygen atom as a hetero atom andoptionally having a substituent); and R_(A) ¹ and R_(A) ² independentlyrepresent a hydrogen atom, an alkyl group, a haloalkyl group, or an arylgroup, and R_(A) ¹ and R_(A) ² each may have the same or differentsubstituents.
 27. The chromophore according to claim 1, wherein thechromophore is represented by the formula IV-2-b:

wherein n represents an integer of 1 to 5; at least one of R_(D) ¹,R_(D) ², and R_(D) ³ independently represents an alkoxy group, anaryloxy group, an aralkyloxy group, a silyloxy group, an alkenyloxygroup, an alkenylcarbonyloxy group, an alkynyloxy group, or a hydroxygroup; the rest independently represent a hydrogen atom or an alkylgroup; and R_(D) ¹, R_(D) ², and R_(D) ³ each may have the same ordifferent substituents (when R_(D) ² and R_(D) ³ are each attached toadjacent carbon atoms of the aryl of the donor structure D, (1) R_(D) ²and R_(D) ³ may form, together with the two adjacent carbon atoms, aring optionally having a substituent; and R_(D) ¹ represents an alkoxygroup, an aryloxy group, an aralkyloxy group, a silyloxy group, analkenyloxy group, an alkenylcarbonyloxy group, an alkynyloxy group, or ahydroxy group, and R_(D) ¹ may have a substituent, or (2) R_(D) ² andR_(D) ³ may form, together with the two adjacent carbon atoms, aheterocyclic ring containing an oxygen atom as a hetero atom andoptionally having a substituent); and R_(A) ¹ and R_(A) ² independentlyrepresent a hydrogen atom, an alkyl group, a haloalkyl group, or an arylgroup, and R_(A) ¹ and R_(A) ² each may have the same or differentsubstituents.
 28. The chromophore according to claim 6; wherein R_(D) ¹represents a C₁₋₆ alkoxy group, a benzyloxy group, a silyloxy group, aC₂₋₆ alkenyloxy group, a C₂₋₆ alkenylcarbonyloxy group, a C₃₋₆alkynyloxy group, or a hydroxy group, and R_(D) ¹ may have asubstituent; and R_(D) ² and R_(D) ³ independently represent a hydrogenatom, a C₁₋₆ alkoxy group, a benzyloxy group, a silyloxy group, a C₂₋₆alkenyloxy group, a C₂₋₆ alkenylcarbonyloxy group, a C₃₋₆ alkynyloxygroup, or a hydroxy group, and R_(D) ² and R_(D) ³ each may have thesame or different substituents.
 29. The chromophore according to claim6, wherein R_(D) ⁴ and R_(D) ⁵ independently represent an alkyl group, ahydroxyalkyl group, or a silyloxyalkyl group, and R_(D) ⁴ and R_(D) ⁵each may have the same or different substituents.
 30. The chromophoreaccording to claim 11, wherein R_(A) ¹ and R_(A) ² independentlyrepresent a methyl group, a trifluoromethyl group, or a phenyl group,and R_(A) ¹ and R_(A) ² each may have the same or differentsubstituents.
 31. The chromophore according to claim 13, wherein π¹ andπ² are each represented by the following formula:

and π¹ and π² each may have the same or different substituents.
 32. Thechromophore according to claim 13, wherein π¹ and π² are represented bythe following formula:

and π¹ and π² each may have the same or different substituents.
 33. Thechromophore according to claim 1, wherein the chromophore is representedby the formula selected from the group consisting of:


34. The chromophore according to claim 1, wherein the chromophore isrepresented by the following formula:


35. The chromophore according to claim 1, wherein the chromophore isrepresented by the formula selected from the group consisting of:


36. The chromophore according to claim 1, wherein the chromophore isrepresented by the formula selected from the group consisting of:


37. The chromophore according to claim 1, wherein the chromophore isrepresented by the formula selected from the group consisting of:


38. The chromophore according to claim 1, wherein the chromophore isrepresented by the formula selected from the group consisting of:


39. The chromophore according to claim 1, wherein the chromophore isrepresented by the following formula:


40. The chromophore according to claim 1, wherein the chromophore isrepresented by the following formula:


41. The chromophore according to claim 1 wherein the chromophore isrepresented by the following formula:


42. A nonlinear optical material comprising the chromophore according toclaim 1 and a host material in which the chromophore is dispersed. 43.The nonlinear optical material according to claim 42, wherein the hostmaterial comprises a resin having a reactive functional group capable offorming a covalent bond with the chromophore, and at least part of thechromophore is attached to the resin.
 44. A nonlinear optical elementhaving a film formed from the chromophore according to claim
 1. 45. Anonlinear optical element having an optical waveguide formed from thechromophore according to claim
 1. 46. A nonlinear optical elementcomprising the chromophore according to claim 1.